Copper heat dissipation material, carrier-attached copper foil, connector, terminal, laminate, shield material, printed-wiring board, metal processed member, electronic device and method for manufacturing the printed wiring board

ABSTRACT

A copper heat dissipation material having a satisfactory heat dissipation performance is provided. The copper heat dissipation material has an alloy layer containing at least one metal selected from Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn and Mo on one or both surfaces, in which surface roughness Sz of the one or both surfaces, measured by a laser microscope using laser light of 405 nm in wavelength, is 5 μm or more.

CROSS REFERENCE TO RELATED APPLICATION

This is a continuation of U.S. application Ser. No. 14/919,357, filedOct. 21, 2015, the entire disclosure of which is incorporated herein byreference.

BACKGROUND OF THE INVENTION Field of the Invention

The present invention relates to a copper heat dissipation material, acarrier-attached copper foil, a terminal, a laminate, a shield material,a printed-wiring board, a metal processed member, an electronic deviceand a method for manufacturing the printed wiring board.

Description of the Related Art

Recently, with the tendency toward miniaturization and high-definitionof electronic devices, it has been concerned that the electronic devicesbreak down with heat generated by the electronic components usedtherein. In particular, in electronic components used in electric carsand hybrid electric cars, which experience remarkable growth, there arecomponents, such as connectors in the battery portion, through whichsignificantly high current flows, and heat generated from the electroniccomponents during current supply has been a matter of concern. In themeantime, in liquid crystals of smart phone tablets and tablets PC, aheat dissipation board called a liquid crystal frame. is used. The heatdissipation board dissipates heat from e.g., liquid crystal componentsand IC chips arranged around the board outside and suppresses break downof electronic components.

CITATION LIST Patent Literature

Patent Literature 1: Japanese Patent Laid-Open No. 07-094644

Patent Literature 2: Japanese Patent Laid-Open No. 08-078461

SUMMARY OF THE INVENTION

Due to the recent tendency of electronic devices described above, liquidcrystal frames conventionally used, however, have failed to satisfy thefunction of dissipating heat from e.g., liquid crystal components and ICchips, such as transition heat, radiation heat and convection heat,outside so as not accumulate heat inside.

Then, an object of the present invention is to provide a copper heatdissipation material having satisfactory heat dissipation performance.

The present inventors intensively conducted studies. As a result, theyfound that a copper heat dissipation material having a satisfactory heatdissipation performance can be provided by forming a surface alloy layercontaining a predetermined metal, simultaneously with controlling thesurface to have a predetermined surface roughness Sz.

The present invention was accomplished based on the above finding.According to an aspect of the invention, there is provided a copper heatdissipation material having an alloy layer containing at least one metalselected from Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn and Mo on one or bothsurfaces, in which surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 5 μm or more.

In an embodiment of the copper heat dissipation material of theinvention, the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 7 μm or more.

In another embodiment of the copper heat dissipation material of theinvention, the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 10 μm or more.

In another embodiment of the copper heat dissipation material of theinvention, the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 14 μm or more.

In another embodiment of the copper heat dissipation material of theinvention, the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 90 μm or less.

In another embodiment of the copper heat dissipation material of theinvention, the surface roughness Sa of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 0.13 μm or more.

In another embodiment of the copper heat dissipation material of theinvention, the surface roughness Sku of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 6 or more.

In another embodiment of the copper heat dissipation material of theinvention, a surface area ratio A/B of surface area A of the one or bothsurfaces to planarly viewed area B, measured by a laser microscope usinglaser light of 405 nm in wavelength, is 1.35 or more.

In another embodiment of the copper heat dissipation material of theinvention, color difference ΔL of the one or both surfaces based onJISZ8730 satisfies ΔL≤−35.

In another embodiment of the copper heat dissipation material of theinvention, color difference Δa of the one or both surfaces based onJISZ8730 satisfies Δa≤15

In another embodiment of the copper heat dissipation material of theinvention, color difference Δb of the one or both surfaces based onJISZ8730 satisfies Δb≤17.

In another embodiment of the copper heat dissipation material of theinvention, the radiation factor of the one or both surfaces is 0.092 ormore.

In another embodiment, the copper heat dissipation material of theinvention comprises a resin layer on the one or both surfaces.

In another embodiment of the copper heat dissipation material of theinvention, the resin layer contains a dielectric substance.

According to another aspect of the present invention, there is provideda carrier-attached copper foil having an intermediate layer and anultra-thin copper layer in this order on one or both surfaces of thecarrier, in which the ultra-thin copper layer is the copper heatdissipation material of the invention.

In one embodiment, the carrier-attached copper foil of the invention hasthe intermediate layer and the ultra-thin copper layer in this order onone of the surfaces of the carrier and a roughened layer on the othersurface of the carrier.

According to another aspect of the present invention, there is provideda connector using the copper heat dissipation material of the invention.

According to another aspect of the present invention, there is provideda terminal using the copper heat dissipation material of the invention.

According to another aspect of the present invention, there is provideda laminate manufactured by laminating the copper heat dissipationmaterial of the invention or the carrier-attached copper foil of theinvention; an optional pressure-sensitive adhesive layer or adhesivelayer; and a resin substrate, a substrate, a chassis, a metal processedmember, an electronic component, an electronic device, a liquid crystalpanel, a display or a separator in this order.

According to another aspect of the present invention, there is provideda shield material having the laminate of the invention.

According to another aspect of the present invention, there is provideda printed-wiring board having the laminate of the invention.

According to another aspect of the present invention, there is provideda metal processed member using the copper heat dissipation material ofthe invention or the carrier-attached copper foil of the invention.

According to another aspect of the present invention, there is providedan electronic device using the copper heat dissipation material of theinvention or the carrier-attached copper foil of the invention.

According to another aspect of the present invention, there is provideda method for manufacturing a printed wiring board, including

a step of preparing the carrier-attached copper foil of the inventionand an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of forming a metal-clad laminate by detaching carrier from thecarrier-attached copper foil after the carrier-attached copper foil andthe insulating substrate are laminated, and thereafter,

a step of forming a circuit by any one of a semi-additive method, asubtractive method, a partly additive method and a modifiedsemi-additive method.

According to another aspect of the present invention, there is provideda method for manufacturing a printed wiring board, including

a step of forming a circuit on the surface of the ultra-thin copperlayer of the carrier-attached copper foil according to according to thepresent invention or the surface of the carrier,

a step of forming a resin layer on the surface of the ultra-thin copperlayer of the carrier-attached copper foil or the surface of the carrierso as to bury the circuit,

a step of forming a circuit on the resin layer

a step of detaching the carrier or the ultra-thin copper layer after thecircuit is formed on the resin layer, and

a step of exposing the circuit buried in the resin layer and formed onthe surface of the ultra-thin copper layer or the surface of the carrierby removing the ultra-thin copper layer or the carrier after the carrieror the ultra-thin copper layer is detached.

According to the present invention, it is possible to provide a copperheat dissipation material having a satisfactory heat dissipationperformance.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic view of a sample according to Example as viewedfrom the above; and

FIG. 2 is schematic cross-sectional view the sample according toExample.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[Configuration of Copper Heat Dissipation Material and ProductionMethod]

As the copper heat dissipation material to be used in the presentinvention, copper or a copper alloy can be used.

As copper, copper having a purity of 95 mass % or more, and morepreferably 99.90 mass % or more is mentioned. Typical examples thereofinclude phosphorus deoxidized copper (JIS H3100, Alloy Nos. C1201,C1220, C1221) defined in JIS H0500 and JIS H3100; oxygen-free copper(JIS H3100, Alloy No. C1020); tough pitch copper (JIS H3100, Alloy No.C1100); and electrolytic copper foil. Alternatively, copper or a copperalloy containing at least one of Sn, Ag, Au, Co, Cr, Fe, In, Ni, P, Si,Te, Ti, Zn, B, Mn and Zr in a total amount of 0.001 to 4.0 mass % can beused.

Examples of the copper alloy further include phosphor bronze, Corsonalloy, red brass, brass, nickel silver and other copper alloys.Alternatively, copper or copper alloys defined in JIS H 3100 to JISH3510, JIS H 5120, JIS H 5121, JIS C 2520 to JIS C 2801 and JIS E 2101to JIS E 2102 can be used in the present invention. Note that, in thespecification, unless otherwise specified, JIS standards mentioned aboveto indicate the standard of metals are those listed in 2001 JISstandard.

Phosphor bronze typically refers to a copper alloy containing copper asa main component and Sn and P (smaller than S in mass). As an example ofthe composition of phosphor bronze, a composition having Sn (3.5 to 11mass %), P (0.03 to 0.35 mass %) and the remainder consisting of copperand unavoidable impurities is mentioned. The phosphor bronze may containelements such as Ni and Zn in a total amount of 1.0 mass % or less.

Corson alloy refers to a copper alloy typically produced by adding anelement (e.g., at least one element of Ni, Co and Cr) which forms acompound with Si and precipitates in the mother phase as a second phaseparticle. As an example of the composition of Corson alloy, acomposition having at least one of Ni, Co and Cr (0.5 to 4.0 mass % intotal), Si (0.1 to 1.3 mass %) and the remainder consisting of copperand unavoidable impurities is mentioned. As another example of thecomposition of Corson alloy, a composition having either one of Ni andCo (0.5 to 4.0 mass % in total), Si (0.1 to 1.3 mass %), Cr (0.03 to 0.5mass %), and the remainder consisting of copper and unavoidableimpurities is mentioned. As another example of the composition of Corsonalloy, a composition having Ni (0.5 to 4.0 mass %), Si (0.1 to 1.3 mass%), Co (0.5 to 2.5 mass %) and the remainder consisting of copper andunavoidable impurities is mentioned. As another example of thecomposition of Corson alloy, a composition having Ni (0.5 to 4.0 mass%), Si (0.1 to 1.3 mass %), Co (0.5 to 2.5 mass %), Cr (0.03 to 0.5 mass%) and the remainder consisting of copper and unavoidable impurities ismentioned. As another examples of the composition of Corson alloy, acomposition having Si (0.2 to 1.3 mass %), Co (0.5 to 2.5 mass %) andthe remainder consisting of copper and unavoidable impurities ismentioned. To the Corson alloys, other elements (for example, Mg, Sn, B,Ti, Mn, Ag, P, Zn, As, Sb, Be, Zr, Al and Fe) may be optionally added.These other optional elements are generally added in a total amount upto about 5.0 mass %. As a further another example of the composition ofCorson alloy, a composition having at least one of Ni, Co and Cr (0.5 to4.0 mass % in total), Si (0.1 to 1.3 mass %), Sn (0.01 to 2.0 mass %),Zn (0.01 to 2.0 mass %) and the remainder consisting of copper andunavoidable impurities is mentioned.

In the present invention, red brass refers to an alloy of copper andzinc containing zinc (1 to 20 mass %) and more preferably zinc (1-10mass %). Furthermore, the red brass may contain tin (0.1 to 1.0 mass %).

In the present invention, brass refers to an alloy of copper and zinc,more specifically a copper alloy containing zinc (20 mass % or more).The upper limit of zinc, although it is not particularly limited, is 60mass % or less, preferably 45 mass % or less or 40 mass % or less.

In the present invention, nickel silver refers to a copper alloycontaining copper (60 mass % to 75 mass %) as a main component, nickel(8.5 mass % to 19.5 mass %) and zinc (10 mass % to 30 mass %).

In the present invention, other copper alloys refer to those containingone or two or more elements of Zn, Sn, Ni, Mg, Fe, Si, P, Co, Mn, Zr,Ag, B, Cr and Ti (8.0% or less in total) and the remainder consisting ofunavoidable impurities and copper.

Note that, the heat dissipation material of the present invention can beprepared by using a metal having a satisfactory heat conductivity suchas aluminum, an aluminum alloy, nickel, a nickel alloy, magnesium, amagnesium alloy, silver, a silver alloy, gold, a gold alloy, a preciousmetal or an alloy containing a precious metal in place of copper or acopper alloy to be used as the copper heat dissipation material. Notethat the metal to be used in the copper heat dissipation material andheat dissipation material preferably has a heat conductivity of 32W/(m·K) or more.

The configuration of the copper heat dissipation material to be used inthe present invention, although it is not particularly limited, may be aprocessed shape into the final electronic component or a partiallyprocessed by pressing. Alternatively, the copper heat dissipationmaterial may not be processed into a shape and may have sheet, plate,strip, foil, rod, line, and box and a three-dimensional shape (cuboid,cube, polyhedron, triangular pyramid, column, cylinder, cone, sphere,roughened three-dimensional body, a three-dimensional body having a flatand/or curved surface). Furthermore, the copper heat dissipationmaterial is preferably a rolled copper foil or an electrolytic copperfoil and more preferably a rolled copper foil. Note that the “copperfoil” is defined to include a copper-alloy foil.

The thickness of the copper heat dissipation material that can be used,although it is not particularly limited, for example, may beappropriately controlled so as to have a suitable thickness dependingupon the use, for example, about 1 to 5000 μm or about 2 to 1000 μm canbe employed. More specifically, if the copper heat dissipation materialto which a circuit is formed and put in use, the thickness thereof is 35μm or less, and if the copper heat dissipation material is used as ashield tape as a shield material, the thickness of the copper heatdissipation material may be as thin as 18 μm or less. If the copper heatdissipation material is used as a connector within an electronic deviceand as a shield material other than a shield tape, as a terminal and acover, the copper heat dissipation material may have a thickness as highas 70 to 1000 μm. Thus, the upper limit thickness is not particularlyspecified. Note that the shield material may be subjected alone toshield use or may be constituted in combination with other componentsand subjected to shield use as a shield component.

In the copper heat dissipation material of the invention, a surfaceroughness Sz (the maximum height of the surface) of one or both surfacesthereof, which is measured by a laser microscope using laser light of405 nm in wavelength, is 5 μm or more. If surface roughness Sz (of oneor both surfaces of the copper heat dissipation material) is less than 5μm, heat is not sufficiently dissipated from the exothermic body. Thesurface roughness Sz (of one or both surfaces of a copper heatdissipation material) is preferably 7 μm or more, more preferably 10 μmor more, further more preferably 14 μm or more, further more preferably15 μm or more and further more preferably 25 μm or more. The upperlimit, although it is not particularly limited, may be, for example, 90μm or less, 80 μm or less or 70 μm or less. If the surface roughness Szexceeds 90 μm, productivity may sometimes decrease.

The “surface” of the copper heat dissipation material herein basicallyrefers to the surface of the alloy layer of the copper heat dissipationmaterial. If a surface treated layer such as a heat-resistant layer, arustproofing layer, a chromate treated layer and a layer treated with asilane coupling agent is provided to the surface of the copper heatdissipation material, the “surface” of the copper heat dissipationmaterial refers to the outermost surface of the surface treated layer.

In the copper heat dissipation material of the invention, a surfaceroughness Sa (arithmetic average surface-roughness) of one or bothsurfaces thereof is preferably 0.13 μm or more. If the surface roughnessSa of one or both surfaces of the copper heat dissipation material isless than 0.13 μm, performance of dissipating heat from an exothermicbody may decrease. The surface roughness Sa (of one or both surfaces ofthe copper heat dissipation material) is more preferably 0.20 μm ormore, further more preferably 0.25 μm or more, further more preferably0.30 μm or more, typically 0.1 to 1.0 μm and more typically 0.1 to 0.9μm.

In the copper heat dissipation material of the invention, a surfaceroughness Sku (peakedness of surface height distribution, i.e.,kurtosis) of one or both surfaces thereof is preferably 6 or more. IfSku (of one or both surfaces thereof) is less than 6, performance ofdissipating heat from an exothermic body may decrease. Sku (of one orboth surfaces thereof) is more preferably 9 or more, further morepreferably 10 or more, further more preferably 40 or more, further morepreferably 60 or more, typically 3 to 200 and more typically 4 to 180.

In the copper heat dissipation material of the invention, a surface arearatio A/B, which is the ratio of surface area A of the one or bothsurfaces to planarly viewed area B, measured by a laser microscope usinglaser light of 405 nm in wavelength, is preferably 1.35 or more. If thesurface area ratio A/B (of one or both surfaces) is less than 1.35, theperformance of dissipating heat from an exothermic body may decrease.The surface area ratio A/B is more preferably 1.36 or more, further morepreferably 1.38 or more, further more preferably 1.40 or more, furthermore preferably 1.45 or more, typically 1.00 to 8.00 and more typically1.10 to 7.50.

In the copper heat dissipation material of the invention, the radiationfactor of one or both surfaces is preferably 0.092 or more. If theradiation factor (of one or both surfaces of the copper heat dissipationmaterial) is 0.092 or more, heat from an exothermic body can besatisfactorily dissipated. The radiation factor (of one or both surfacesof the copper heat dissipation material) is more preferably 0.10 ormore, further more preferably 0.123 or more, further more preferably0.154 or more, further more preferably 0.185 or more and further morepreferably 0.246 or more.

In the copper heat dissipation material of the invention, the upperlimit of the radiation factor (of one or both surfaces), although it isnot necessarily defined, is typically 1 or less, more typically 0.99 orless, more typically 0.95 or less, more typically 0.90 or less, moretypically 0.85 or less and more typically 0.80 or less. Note that if theradiation factor (of one or both surfaces of the copper heat dissipationmaterial) is 0.90 or less, productivity is improved.

In the copper heat dissipation material of the invention, colordifference ΔL of one or both surfaces, which is color difference basedon the object color of a white plate (when D65 is used as a light sourceand a field of view is set to have a viewing angle of 10°, thetristimulus values of the X₁₀Y₁₀Z₁₀ color system (JIS Z8701 1999) of thewhite plate are X₁₀=80.7, Y₁₀=85.6, Z₁₀=91.5 and the object color of thewhite plate in the L*a*b color system is expressed by L*=94.14,a*=−0.90, b*=0.24) as a reference color; in other words, colordifference ΔL defined in JISZ8730 (difference of CIE luminosity L*between colors of two objects in the L*a*b* color system defined in JISZ8729 (2004)), preferably satisfies ΔL≤−35. Likewise, if the colordifference ΔL of the surface of a copper heat dissipation materialsatisfies ΔL≤−35, heat from an exothermic body, such as conductive heat,radiant heat and convection heat, can be satisfactorily absorbed anddissipated. Surface color difference ΔL more preferably satisfiesΔL≤−40, further more preferably ΔL≤−45, further more preferably ΔL≤−50,further more preferably ΔL≤−60, further more preferably ΔL≤−70, andtypically −90≤ΔL≤−5, −90≤ΔL≤−10, ≤88≤ΔL≤−35, or −85≤ΔL≤−35.

In the copper heat dissipation material of the invention, colordifference Δa of one or both surfaces, which is color difference basedon the object color of a white plate (when D65 is used as a light sourceand a field of view is set to have a viewing angle of 10°, thetristimulus values of the X₁₀Y₁₀Z₁₀ color system (JIS Z8701 1999) of thewhite plate are X₁₀=80.7, Y₁₀=85.6, Z₁₀=91.5 and the object color of thewhite plate of the L*a*b* color system is expressed by L*=94.14,a*=−0.90, b*=0.24) as a reference color; in other words, colordifference Δa defined in JISZ8730 (difference of color coordinate, a*between colors of two objects in the L*a*b* color system defined in JISZ8729 (2004)), preferably satisfies Δa≤15. Likewise, if the colordifference Δa of the surface of a copper heat dissipation materialsatisfies Δa≤15, heat from an exothermic body, such as conductive heat,radiant heat and convection heat, can be satisfactorily absorbed. Thesurface color difference Δa is more preferably Δa≤10, further morepreferably Δa≤5, further more preferably Δa≤4, typically −10≤Δa≤15 andmore typically −8≤Δa≤15.

In the copper heat dissipation material of the invention, colordifference Δb of one or both surfaces, which is color difference basedon the object color of a white plate (when D65 is used as a light sourceand a field of view is set to have a viewing angle of 100, thetristimulus values of the X₁₀Y₁₀Z₁₀ color system (JIS Z8701 1999) of thewhite plate are X₁₀=80.7, Y₁₀=85.6, Z₁₀=91.5 and the object color of thewhite plate of the L*a*b* color system is expressed by L*=94.14,a*=−0.90, b*=0.24) as a reference color; in other words, colordifference Δb defined in JISZ8730 (difference of color coordinate, b*between colors of two objects in the L*a*b* color system defined in JISZ8729 (2004)), preferably satisfies Δb≤17. Likewise, if the colordifference Δb of the surface of a copper heat dissipation materialsatisfies Δb≤17, heat from an exothermic body, such as conductive heat,radiant heat and convection heat, can be satisfactorily absorbed. Thesurface color difference Δb is more preferably Δb≤15, further morepreferably Δb≤5, further more preferably Δb≤3, typically −15≤Δb≤17 andmore typically −10≤Δb≤17.

In the copper heat dissipation material of the invention, colordifference ΔE*ab of one or both surfaces, which is color differencebased on the object color of a white plate (when D65 is used as a lightsource and a field of view is set to have a viewing angle of 10°, thetristimulus values of the X₁₀Y₁₀Z₁₀ color system (JIS Z8701 1999) of thewhite plate are X₁₀=80.7, Y₁₀=85.6, Z₁₀=91.5 and the object color of thewhite plate of the L*a*b* color system is expressed by L*=94.14,a*=−0.90, b*=0.24) as a reference color; in other words, colordifference ΔE*ab defined in JISZ8730 preferably satisfies 47≤ΔE*ab.Likewise, if the color difference ΔE*ab of the surface of a copper heatdissipation material satisfies 47≤ΔE*ab, heat from an exothermic body,such as conductive heat, radiant heat and convection heat, can besatisfactorily absorbed. The surface color difference ΔE*ab is morepreferably 50≤ΔE*ab, further more preferably 55≤ΔE*ab, further morepreferably 60≤ΔE*ab, further more preferably 71≤ΔE*ab, typically 47ΔE*ab≤90, more typically 47≤ΔE*ab≤88 and more typically 47≤ΔE*ab≤85.

Color differences ΔL, Δa and Δb, each of which are measured by acolor-difference meter, are general indexes represented by the L*a*b*color system based on JIS Z8730 (2009) in consideration of furtherblack/white/red/green/yellow/blue and ΔL represents black-white colordifference, Δa red-green color difference and Δb Yellow Blue colordifference. ΔE*ab is represented by the following expression using thesecolor differences. The color differences (ΔL, Δa, Δb) can be measured byuse of a color difference meter, MiniScan XE Plus manufactured byHunterLab.ΔE*ab=√{square root over (ΔL ² +Δa ² +Δb ²)}  Expression 1

The copper heat dissipation material of the invention has an alloy layercontaining at least one metal selected from Cu, Co, Ni, W, P, Zn, Cr,Fe, Sn and Mo on one or both surfaces. With such a configuration, theaforementioned color difference and surface roughness can be controlled.If color difference is controlled, heat from an exothermic body, such asconductive heat, radiant heat and convection heat, can be satisfactorilyabsorbed. Note that the alloy layer can be formed by wet plating such aselectroplating, non-electrolytic plating and immersion plating;sputtering; or dry plating such as CVD and PDV. In view of cost,electroplating is preferable.

The alloy layer of the copper heat dissipation material of the inventioncan be formed, for example, in the following plating conditions alone orin combination and by controlling the number of treatment operations.Note that the remainder of the treatment liquid to be used in desmeartreatment, electrolytic, surface treatment or plating is water unlessotherwise specified.

Plating Condition 1 for Forming Alloy Layer 1: Cu Layer

Plating liquid composition: Cu concentration 5 to 20 g/L

PH: 1.0 to 5.0

Temperature: 25 to 55° C.

Current density: 2 to 70 A/dm²

Plating time: 0.2 to 20 seconds

Plating Condition 2 for Forming Alloy Layer: Cu—Co—Ni Layer

Plating liquid composition: Cu concentration 10 to 20 g/L, Coconcentration 5 to 10 g/L, Ni concentration 5 to 10 g/L

PH: 2.0 to 6.0

Temperature: 25 to 55° C.

Current density: 10 to 60 A/dm²

Plating time: 0.3 to 10 seconds

Plating Condition 3 for Forming Alloy Layer: Cu—Co—Ni—P Layer

Plating liquid composition: Cu concentration 10 to 20 g/L, Coconcentration 5 to 10 g/L, Ni concentration 5 to 10 g/L, P concentration10 to 800 mg/L

PH: 2.0 to 6.0

Temperature: 25 to 55° C.

Current density: 10 to 60 A/dm²

Plating time: 0.3 to 10 seconds

Plating Condition 4 for Forming Alloy Layer: Ni—Zn Layer

Plating liquid composition: Ni concentration 10 to 60 g/L, Znconcentration 5 to 30 g/L

PH: 3.5 to 6.0

Temperature: 25 to 55° C.

Current density: 0.2 to 3.0 A/dm²

Plating time: 4 to 181 seconds

Plating Condition 5 for Forming Alloy Layer: Cu—Ni—P Layer

Plating liquid composition: Cu concentration 5 to 15 g/L, Niconcentration 10 to 30 g/L, P concentration 10 to 800 m g/L

PH: 2.0 to 5.0

-   -   Temperature: 25 to 55° C.    -   Current density: 10 to 60 A/dm²    -   Plating time: 0.2 to 10 seconds

when an alloy layer is formed in Plating conditions 1 to 3 and 5, it isnecessary to perform a surface treatment a plurality of times.

Plating Condition 6 for Forming Alloy Layer: Cr—Zn Layer

Plating liquid composition: Cr concentration 2 to 8 g/L, Znconcentration 0.1 to 1.0 g/L

PH: 2.0 to 4.0

Temperature: 40 to 60° C.

Current density: 0.5 to 3.0 A/dm²

Plating time: 0.2 to 10 seconds

Plating Condition 7 for Forming Alloy Layer: Cu—Ni—W Layer

Plating liquid composition: Cu concentration 5 to 15 g/L, Niconcentration 10 to 40 g/L, W concentration 10 to 1000 m g/L

PH: 2.0 to 4.0

Temperature: 40 to 60° C.

Current density: 10 to 60 A/dm²

Plating time: 0.2 to 10 seconds

Plating Condition 8 for Forming Alloy Layer: Ni—W—Sn Layer

Plating liquid composition: Ni concentration 10 to 50 g/L, Wconcentration 300 to 3000 m g/L, Sn concentration 100 to 1000 m g/L

PH: 3.0 to 6.5

Temperature: 40 to 60° C.

Current density: 0.1 to 4.0 A/dm

Plating time: 10-60 seconds

Plating Condition 9 for Forming Alloy Layer: Cu—Ni—Mo—Fe Layer

Plating liquid composition: Cu concentration 5 to 15 g/L, Niconcentration 10 to 40 g/L, Mo concentration 50 to 5000 m g/L, Feconcentration 0.5 to 5.0 g/L

PH: 2.0 to 5.0

Temperature: 40 to 60° C.

Current density: 10 to 60 A/dm²

Plating time: 5-30 seconds

Note that additives known in the art may be used in the plating liquidfor forming an alloy layer. For example, an additive acceleratingprecipitation of metal ions, an additive for stabilizing metal ions in aplating liquid, an additive permitting metal ions to uniformlyprecipitate, and a labelling agent and a glazing agent may be used.

As the additive, for example, chlorine, bis(3-sulfopropyl)disulfide, anamine compound, glue, cellulose, ethylene glycol, thiourea, a sulfideand an organic sulfur compound. As the concentration of the additive, aconcentration usually used is preferable. If the additive is added, thecolor tone and unevenness of a surface can be controlled.

When the alloy layer is used, the total amount deposited of at least onemetal selected from Co, Ni, W, P, Zn, Cr, Fe, Sn and Mo and contained inthe alloy layer is preferably 0.1 to 100000 μg/dm², preferably, 5 to80000 μg/dm², preferably 10 to 85000 μg/dm², and preferably 100 to 80000μg/dm². If the total amount deposited is lower than 0.1 μg/dm², theeffect of the alloy layer provided may be low. In contrast, if the totalamount deposited exceeds 100000 μg/dm², productivity may reduce. When acircuit is formed in the copper heat dissipation material and ahigh-frequency signal is sent by use of the circuit, the upper limit ofthe amount deposited of Ni contained in the alloy layer can bepreferably 4000 μg/dm² or less, more preferably 3000 μg/dm² or less,more preferably 1400 μg/dm² or less and more preferably 1000 μg/dm² orless. The lower limit of the amount deposited of Ni can be typically 50μg/dm² or more, more preferably 100 μg/dm² and more preferably 300μg/dm² or more. In short, the amount deposited of Ni contained in thealloy layer is typically 50 μg/dm² or more and 4000 μg/dm² or less.

In the case where a circuit is formed in the copper heat dissipationmaterial and a high-frequency signal is sent by use of the circuit, theupper limits of the amounts deposited of Co, Fe and Mo contained in theabove alloy layer each are preferably 6000 μg/dm² or less, morepreferably 5000 μg/dm² or less, more preferably 3000 μg/dm² or less,more preferably 2400 μg/dm² or less and more preferably 2000 μg/dm² orless. The lower limit of the amount deposited of Co can be typically 50μg/dm² or more, more preferably 100 μg/dm² and more preferably 300μg/dm² or more. In other words, the amount deposited of Co contained inthe alloy layer is typically 50 μg/dm² or more and 6000 μg/dm² or less.In the case where the above alloy layer has a layer containing Co and/orNi other than the Cu—Co—Ni alloy plating layer, the total amountdeposited of Ni and the total amount deposited of Co in the whole alloylayer can be set to fall within the aforementioned range.

When Cu is contained the above alloy layer, the upper limit, although itis not particularly necessary to set, is typically 100 mg/dm² or less,more typically 90 mg/dm² or less and more typically 80 mg/dm² or less.In the case where Cu is contained in the above alloy layer, the lowerlimit, although it is not particularly necessary to set, is typically0.01 μg/dm² or more, more typically 0.1 μg/dm² or more and moretypically 1 μg/dm² or more, and typically 0.01 μg/dm² or more and 100mg/dm² or less.

On the surface of copper or a copper alloy or the surface of an alloylayer to be used as a copper heat dissipation material, a surfacetreated layer may be provided. The surface treated layer may be aroughened layer, a heat-resistant layer, a rustproofing layer, achromate treated layer, a layer treated with a silane coupling agent ora plated layer. The surface treated layer may be formed by forming ablack resin layer on the surface of a copper heat dissipation material.More specifically, the black resin layer can be formed by impregnatinge.g., an epoxy resin, with a black paint and applying the resin to acopper heat dissipation material followed by drying so as to obtain apredetermined thickness.

Surface Treated Layer

A roughened layer may be provided to the surface of copper or the copperalloy or the surface of the alloy layer to be used as a copper heatdissipation material by applying a roughening treatment to the surfacein order to improve adhesion to, for example, an adhesive layer. Theroughening treatment can be applied by forming roughening particles ofe.g., copper or a copper alloy. The roughening particles may be small.The roughened layer may be a layer formed of an element selected fromthe group consisting of copper, nickel, cobalt, phosphorus, tungsten,arsenic, molybdenum, chromium and zinc or an alloy containing at leastone of these. Alternatively, in the roughening treatment, rougheningparticles of copper or a copper alloy are formed, and then secondaryparticles or tertiary particles formed of e.g., nickel, cobalt, copperand zinc or an alloy of these are provided. Thereafter, a heat-resistantlayer or a rustproofing layer may be formed of e.g., nickel, cobalt,copper, zinc or an alloy of these. Furthermore, the surface thereof maybe treated with chromate and a silane coupling agent. Alternatively, aroughening treatment is not applied and a heat-resistant layer or arustproofing layer is formed of, e.g., nickel, cobalt, copper and zincor an alloy of these and the resultant surface may be treated withchromate and a silane coupling agent. In other words, to the surface ofthe roughened layer or alloy layer, at least one layer selected from thegroup consisting of a heat-resistant layer, a rustproofing layer, achromate treated layer and a layer treated with a silane coupling agentmay be formed; or at least one layer selected from the group consistingof a heat-resistant layer, a rustproofing layer, a chromate treatedlayer and a layer treated with a silane coupling agent may be formed onthe surface of copper or a copper alloy to be used as a copper heatdissipation material. Note that the aforementioned heat-resistant layer,rustproofing layer, chromate treated layer and layer treated with asilane coupling agent are each formed of a plurality of layers (forexample, two layers or more, three layers or more).

The chromate treated layer herein refers to a layer treated with asolution containing chromic anhydride, chromic acid, dichromate,chromate or dichromate. The chromate treated layer may contain anelement such as cobalt, iron, nickel, molybdenum, zinc, tantalum,copper, aluminum, phosphorus, tungsten, tin, arsenic and titanium (inany form such as a metal, an alloy, an oxide, a nitride and a sulfide).Examples of the chromate treated layer include a chromate treated layerobtained by treatment with chromic anhydride or an aqueous potassiumdichromate solution and a chromate treated layer obtained by treatmentwith a liquid containing chromic anhydride or potassium dichromate andzinc.

As the heat-resistant layer and rustproofing layer, a heat-resistantlayer and a rustproofing layer known in the art can be used. Forexample, the heat-resistant layer and/or rustproofing layer may be alayer containing at least one element selected from the group consistingof nickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus,arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinumgroup elements, iron and tantalum; or a metal layer or alloy layerformed of at least one element selected from the group consisting ofnickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus,arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinumgroup elements, iron and tantalum. The heat-resistant layer and/orrustproofing layer may contain an oxide, a nitride and/or a silicidecontaining at least one element selected from the group consisting ofnickel, zinc, tin, cobalt, molybdenum, copper, tungsten, phosphorus,arsenic, chromium, vanadium, titanium, aluminum, gold, silver, platinumgroup elements, iron and tantalum. Alternatively, the heat-resistantlayer and/or rustproofing layer contain a nickel-zinc alloy or may be anickel-zinc alloy layer. The nickel-zinc alloy layer may contain nickel(50 wt % to 99 wt %) and zinc (50 wt % to 1 wt %) except unavoidableimpurities. The total amount deposited of zinc and nickel in thenickel-zinc alloy layer may be 5 to 1000 mg/m², preferably 10 to 500mg/m², and preferably 20 to 100 mg/m². The ratio of the amount depositedof nickel to the amount deposited of zinc, i.e., the amount deposited ofnickel/the amount deposited of zinc, in the layer containing anickel-zinc alloy or the nickel-zinc alloy layer, is preferably 1.5 to10. The amount deposited of nickel of the layer containing a nickel-zincalloy or the nickel-zinc alloy layer is preferably 0.5 mg/m² to 500mg/m² and more preferably 1 mg/m² to 50 mg/m². In the case where theheat-resistant layer and/or rustproofing layer is a layer containing anickel-zinc alloy, when the inner wall of e.g., through-holes andvia-holes comes into contact with a desmear liquid, the interfacebetween copper or a copper alloy or an alloy layer and a resin substrateis rarely eroded by the desmear liquid, with the result thatadhesiveness between the copper or copper alloy or alloy layer and theresin substrate improves.

The heat-resistant layer and/or rustproofing layer may be, for example,a laminate obtained by sequentially laminating a nickel or nickel alloylayer, which has an amount deposited of 1 mg/m² to 100 mg/m², preferably5 mg/m² to 50 mg/m², and a tin layer, which has an amount deposited of 1mg/m² to 80 mg/m², preferably 5 mg/m² to 40 mg/m². The nickel alloylayer may be constituted of any one of nickel-molybdenum, nickel-zincand nickel-molybdenum-cobalt. In the heat-resistant layer and/orrustproofing layer, the total amount deposited of nickel or a nickelalloy and tin is preferably 2 mg/m² to 150 mg/m² and more preferably 10mg/m² to 70 mg/m². In the heat-resistant layer and/or rustproofinglayer, [amount deposited of nickel or nickel in a nickel alloy]/[amountdeposited of tin] is preferably 0.25 to 10 and more preferably 0.33 to3. If the heat-resistant layer and/or rustproofing layer is used, when acarrier-attached copper foil is processed into a printed-wiring board,the resultant peel strength of a circuit, the degree of deterioration ofchemical resistance of the peel strength, and the like are improved.

Note that as a silane coupling agent to be used in the silane couplingtreatment, a silane coupling agent known in the art may be used; forexample, an amino-based silane coupling agent, an epoxy-based silanecoupling agent or a mercapto-based silane coupling agent may be used.Specific examples of the silane coupling agent may include vinyltrimethoxy silane, vinylphenyl trimethoxysilane,γ-methacryloxypropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane,4-glycidyl butyl trimethoxysilane, γ-aminopropyltriethoxysilane,N-β(aminoethyl) γ-aminopropyltrimethoxysilane,N-3-(4-(3-amino-propoxy)butoxy)propyl-3-aminopropyltrimethoxysilane,imidazole silane, triazine silane and γ-mercaptopropyltrimethoxysilane.

The layer treated with a silane coupling agent may be formed of a silanecoupling agent such as an epoxy silane, amino silane, methacryloxysilane and a mercapto-based silane. Note that such silane couplingagents may be used as a mixture of two or more types. Of them, the layertreated with a silane coupling agent is preferably formed of anamino-based silane coupling agent or an epoxy-based silane couplingagent.

The amino-based silane coupling agent herein may be selected from thegroup consisting of N-(2-aminoethyl)-3-aminopropyltrimethoxysilane,3-(N-styrylmethyl-2-aminoethyl amino)propyl trimethoxysilane,3-aminopropyltriethoxysilane,bis(2-hydroxy-ethyl)-3-aminopropyltriethoxysilane,aminopropyltrimethoxysilane, N-methyl-aminopropyltrimethoxysilane,N-phenyl-aminopropyltrimethoxysilane,N-(3-acryloxy-2-hydroxypropyl)-3-aminopropyltriethoxysilane,4-aminobutyltriethoxysilane, (aminoethylaminomethyl)phenethyl trimethoxysilane, N-(2-aminoethyl-3-aminopropyl)trimethoxysilane,N-(2-aminoethyl-3-aminopropyl)tris(2-ethylhexoxy)silane,6-(aminohexylaminopropyl)trimethoxysilane, aminophenyitrimethoxysilane,3-(1-amino-propoxy)-3,3-dimethyl-1-propenyltrimethoxysilane,3-aminopropyl tris(methoxyethoxy)silane, 3-aminopropyltriethoxysilane,3-aminopropyltrimethoxysilane, ω-amino undecyl trimethoxysilane,3-(2-N-benzylaminoethylaminopropyl)trimethoxy silane,bis(2-hydroxyethyl)-3-aminopropyltriethoxysilane,(N,N-diethyl-3-aminopropyl)trimethoxysilane,(N,N-dimethyl-3-amino-propyl)trimethoxysilane,N-methyl-aminopropyltrimethoxysilane,N-phenyl-aminopropyltrimethoxysilane,3-(N-styrylmethyl-2-aminoethylamino)propyltrimethoxysilane,γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane andN-3-(4-(3-amino-propoxy)butoxy)propyl-3-aminopropyltrimethoxysilane.

It is desirable that the layer treated with a silane coupling agent isprovided so as to satisfy the range of 0.05 mg/m² to 200 mg/m²,preferably 0.15 mg/m² to 20 mg/m² and preferably 0.3 mg/m² to 2.0 mg/m²in terms of silicon atom. In the above-mentioned range, adhesivenessbetween copper or a copper alloy, or an alloy layer to be used in acopper heat dissipation material and an adhesive layer can be improved.

To the surface of copper or the copper alloy, or the alloy layer to beused as the copper heat dissipation material, a roughened layer, aheat-resistant layer, a rustproofing layer, a layer treated with asilane coupling agent or a chromate treated layer, a surface treatmentdescribed in International Publication No. WO2008/053878, JapanesePatent Laid-Open No. 2008-111169, Japanese Patent No. 5024930,International Publication No. WO2006/028207, Japanese Patent No.4828427, International Publication No. WO2006/134868, Japanese PatentNo. 5046927, International Publication No. WO2007/105635, JapanesePatent No. 5180815, Japanese Patent Laid-Open No. 2013-19056, can beapplied.

In the copper heat dissipation material of the invention, the surface ofthe copper substrate on which the aforementioned alloy layer is to beprovided is controlled as follows. This is because the surface of thecopper heat dissipation material is controlled to have predetermined Sz,Sa and Sku, ΔE*ab, ΔL, Δa, Δb and surface area ratio.

When a rolled material is used as the copper substrate, the rolledmaterial is obtained by rolling while controlling the oil filmequivalent represented by the following expression.Oil film equivalent={(rolling oil viscosity [cSt])×(sheet passing speed[mpm]+roll peripheral speed [mpm])}/{(bite angle of the roll[rad])×(yield stress of the material [kg/mm²])}

The rolling oil viscosity [cSt] refers to the kinetic viscosity at 40°C.

More specifically, the rolled material, which is obtained by rollingwhile setting an oil film equivalent in the final cold rolling at 16000to 30000, is used as the copper substrate of the present invention. Thisis because, if the oil film equivalent is less than 16000 and beyond30000, the surface of the copper heat dissipation material having theaforementioned alloy layer does not satisfy the predetermined range. Ifthe oil film equivalent Is less than 16000, the value Sz sometimesbecomes excessively low. In contrast, if the oil film equivalent isbeyond 30000, the value Sz sometimes becomes excessively large.

In order to control the oil film equivalent to fall within the range of16000 to 30000, a known method such as a method of using a low viscosityrolling or a method of decreasing a threading speed may be used.

Conditions for manufacturing the electrolytic copper foil that can beused in the invention of the present application are shown below.

Electrolyte Composition

Copper: 90 to 110 g/L

Sulfuric acid: 90 to 110 g/L

Chlorine: 50 to 100 ppm

Leveling agent 1 (bis(3-sulfopropyl)disulfide): 10 to 30 ppm

Leveling agent 2 (amine compound): 10 to 30 ppm

As the above amine compound, an amine compound represented by thefollowing chemical formula can be used.

(where R₁ and R₂ each are selected from the group consisting of ahydroxyalkyl group, an ether group, an aryl group, anaromatic-substituted alkyl group, an unsaturated hydrocarbon group andan alkyl group)

Manufacturing Conditions

Current density: 70 to 100 A/dm²

Electrolyte temperature: 50 to 60° C.

Electrolyte line speed: 3 to 5 m/sec

Electrolysis time: 0.5 to 10 minutes

Note that the state of the surface of copper or a copper alloy to beused in the copper heat dissipation material may be controlled by thefollowing treatment. As the surface treatment, a roughening treatmentmay be applied to the surface of copper or a copper alloy. As theroughening treatment (applied to the surface of copper or a copperalloy), a surface treatment by chemical polishing and electrolyticpolishing may be employed. As the treatment liquid for use in chemicalpolishing, a liquid usually used for etching, such as an etchingsolution containing sulfuric acid and hydrogen peroxide, an etchingsolution containing ammonium fluoride, an etching solution containingsodium persulfate, an etching solution containing ferric chloride orcupric chloride or an etching solution known in the art may be used.Alternatively, the surface of copper or a copper alloy can be roughenedby electrolytic polishing, which is performed, for example, in asolution constituted of copper sulfate and an aqueous sulfuric acidsolution. The electrolytic polishing is generally performed forsmoothing a surface; however, electrolytic polishing is used forroughening the surface in the treatment for the surface of copper or acopper alloy used in the copper heat dissipation material of theinvention. The technical idea used herein is opposite to the general,one. As a method for roughening a surface by electrolytic polishing, aknown technique may be employed. As the known technique of electrolyticpolishing for roughening the surface, those described in Japanese PatentLaid-Open No. 2005-240132, Japanese Patent Laid-Open No. 2010-059547 andJapanese Patent Laid-Open No. 2010-047842, are mentioned. Specificconditions for roughening a surface by electrolytic polishing are, forexample, as follows:

Treatment solution: Cu: 10 to 40 g/L, H₂SO₄: 50 to 150 g/L, temperature:30 to 70° C.

Electrolytic polishing current: 5 to 40 A/dm²

Electrolytic polishing time: 5 to 50 seconds.

As the roughening treatment for the surface of copper or a copper alloy,for example, mechanical polishing of the surface of copper or a copperalloy may be mentioned. Techniques known in the art may be used for themechanical polishing.

Note that after the surface of copper or a copper alloy used in thecopper heat dissipation material of the invention is treated, aheat-resistant layer, a rustproofing layer and a weather-resistant layermay be provided. The heat-resistant layer, rustproofing layer andweather-resistant layer may be provided by methods described above,methods described in Examples and known technical methods.

In the copper heat dissipation material of the invention, on the surfaceof the alloy layer of the copper heat dissipation material, further, asurface treated layer such as a roughened layer, a heat-resistant layer,a rustproofing layer and an oxide layer (the oxide layer is formed onthe surface of the copper heat dissipation material by e.g., heating)may be formed. Between the copper heat dissipation material and thealloy layer, an underlying layer may be provided as long as the platingfor forming the alloy layer is not damaged.

The copper heat dissipation material of the invention is bonded to aresin substrate to produce a laminate serving a shield material such asa shield tape and shield components. If necessary, the copper heatdissipation material can be further processed to form a circuit toproduce, e.g., a printed-wiring board. Examples of the resin substratethat can be used for a rigid PWB (printed-wiring board) include a paperbased phenol resin, a paper based epoxy resin, a synthetic fiber clothbased epoxy resin, a cloth impregnated with a fluorine resin, a glasscloth/paper composite based epoxy resin, a glass cloth/non-woven glasscloth composite based epoxy resin and a glass cloth based epoxy resin.Examples of the resin substrate that can be used for an FPC (flexibleprinted circuit) and tapes include a polyester film and polyimide film,a liquid crystal polymer (LCP) and a PET film. Note that in the presentinvention, the “printed-wiring board” is defined to include aprinted-wiring board provided with components, a circuit board and aprinted board. Two or more printed wiring boards of the presentinvention can be connected to produce a printed-wiring board.Furthermore, at least one printed wiring board of the present inventionand another printed wiring board of the present invention or aprinted-wiring board except the printed wiring board of the presentinvention may be connected and used to form electronic devices. Notethat, in the present invention, the “copper circuit” is defined toinclude a copper wiring.

The copper heat dissipation material of the invention can be used in aheat dissipation board, a structural plate, a shield material, a shieldplate, a shield component, a reinforcing material, a cover, a housing, acase and box to produce metal processed members. Since the copper heatdissipation material of the invention has satisfactory heatabsorbability from an exothermic body and satisfactory dissipation ofheat which the material absorbed, in other words, since the copper heatdissipation material of the invention is extremely excellent in heatdissipation, the copper heat dissipation material is particularlypreferably used as a heat dissipation board. The metal processed memberis defined to include a heat dissipation board, a structural plate, ashield material, a shield plate, a shield component, a reinforcingmaterial, a cover, a housing, a cases and a box.

The metal processed members manufactured by using the copper heatdissipation material of the invention in a heat dissipation board, astructural plate, a shield material, a shield plate, a shield component,a reinforcing material, a cover, a housing, a cases and a box can beused in electronic devices.

Carrier-Attached Copper Foil

A carrier-attached copper foil according to another embodiment of thepresent invention has an intermediate layer and an ultra-thin copperlayer laminated in this order on one or both surfaces of a carrier. Theultra-thin copper layer corresponds to the copper heat dissipationmaterial of the aforementioned embodiment of the present invention. The“copper foil” of the carrier-attached copper foil include a copper-alloyfoil.

Carrier

The carrier that can be used in the present invention is typically ametal foil or a resin film and provided in the form of e.g., a copperfoil, a copper-alloy foil, a nickel foil, a nickel-alloy foil, an ironfoil, an iron-alloy foil, a stainless steel foil, an aluminum foil, analuminum-alloy foil or an insulating resin film (e.g., a polyimide film,a liquid crystal polymer (LCP) film, a polyethylene terephthalate (PET)film, a polyamide film, a polyester film, a fluororesin film).

As the carrier that can be used in the present invention copper foil, acopper foil is preferably used. This is because the copper foil has ahigh electrical conductivity and makes it easy to form the followingintermediate layer and the ultra-thin copper layer. The carrier istypically provided in the form of a rolled copper foil and anelectrolytic copper foil. The electrolytic copper foil is generallyproduced by electrical precipitation of copper on a drum formed oftitanium and stainless steel from a copper sulfate plating bath, whereasthe rolled copper foil is produced by repeating plastic working by amill roll and heat treatment. As the material for a copper foil, notonly high-purity copper such as tough pitch copper and oxygen-freecopper but also a copper alloy such as Sn-containing copper,Ag-containing copper, a copper alloy containing e.g., Cr, Zr or Mg, anda Corson copper alloy containing e.g., Ni and Si can be used.

The thickness of the carrier that can be used in the present invention,although it is not particularly limited, may be controlled to be such anappropriate thickness that allows the carrier to play a role, forexample, 5 μm or more. However, if the thickness is extremely large, theproduction cost increases. Thus, generally, the thickness of the carrieris preferably 35 μm or less. Accordingly, the thickness of the carrieris typically 12 to 70 μm and more typically 18 to 35 μm.

After surface treatment, Sz, Sa and Sku and surface area ratio A/B ofthe surface of the ultra-thin copper layer can be controlled by the samesurface treatment as in the aforementioned copper heat dissipationmaterial.

The electrolytic copper foil that can be manufactured by the followingmethod can be used as a carrier.

Electrolyte Composition

Copper: 90 to 110 g/L

Sulfuric acid: 90 to 110 g/L

Chlorine: 50 to 100 ppm

Leveling agent 1 (bis(3-sulfopropyl)disulfide): 10 to 30 ppm

Leveling agent 2 (amine compound): 10 to 30 ppm

As the above amine compound, an amine compound represented by thefollowing chemical formula can be used.

(where R₁ and R₂ each are selected from the group consisting of ahydroxyalkyl group, an ether group, an aryl group, anaromatic-substituted alkyl group, an unsaturated hydrocarbon group andan alkyl group)

Manufacturing Conditions

Current density: 70 to 100 A/dm²

Electrolyte temperature: 50 to 60° C.

Electrolyte line speed: 3 to 5 m/sec

Electrolysis time: 0.5 to 10 minutes (controlled in accordance with thethickness of copper to be precipitated and current density)

Note that a roughened layer may be provided to the surface of thecarrier, which is opposite to the surface on which an ultra-thin copperlayer is to be provided. The roughened layer may be provided by a methodknown in the art or by the aforementioned roughening treatment.Providing the roughened layer onto the surface of the carrier oppositeto the surface on which an ultra-thin copper layer to be provided, hasan advantage: when the carrier is laminated on a support such as a resinsubstrate from the side of the surface having the roughened layer, thecarrier and the resin substrate are hardly detached.

Intermediate Layer

An intermediate layer is provided on the carrier. Another layer may beprovided between the carrier and the intermediate layer. Theintermediate layer to be used in the invention is not particularlylimited as long as the ultra-thin copper layer is not easily detachedfrom the carrier until a carrier-attached copper foil is laminated on aninsulating substrate; whereas the ultra-thin copper layer is easilydetached from the carrier after the carrier-attached copper foil islaminated on an insulating substrate. The intermediate layer of thecarrier-attached copper foil of the invention may contain, for example,at least one element selected from the group consisting of Cr, Ni, Co,Fe, Mo, Ti, W, P, Cu, Al, Zn, an alloy thereof, a hydrate thereof, anoxide thereof and an organic compound. Furthermore, the intermediatelayer may be formed of a plurality of layers.

For example, the intermediate layer can be constituted by forming asingle metal layer formed of a single element selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn or forming analloy layer formed of at least one element selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, on thecarrier; and then, on the resultant structure, forming a layer formed ofa hydrate or an oxide of at least one element selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn or a layerformed of an organic compound.

Alternatively, the intermediate layer can be constituted by forming asingle metal layer formed of a single element selected from the groupconsisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn or an alloylayer formed of at least one element selected from the group consistingof Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu, Al and Zn, on the carrier, andthen, on the resultant structure, forming a single metal layer formed ofan element selected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti,W, P, Cu, Al and Zn or an alloy layer formed of at least one elementselected from the group consisting of Cr, Ni, Co, Fe, Mo, Ti, W, P, Cu,Al and Zn.

As the organic substance, a known organic substance can be used in theintermediate layer. Preferably, at least any one of anitrogen-containing organic compound, a sulfur-containing organiccompound and a carboxylic acid, is used. Specific examples of thenitrogen-containing organic compound that is preferably used includetriazole compounds having a substituent, such as 1,2,3-benzotriazole,carboxybenzotriazole, N′,N′-bis(benzotriazolylmethyl)urea,1H-1,2,4-triazole and 3-amino-1H-1,2,4-triazole.

Examples of the sulfur-containing organic compound that is preferablyused include mercaptobenzothiazole, 2-mercaptobenzothiazole sodium,thiocyanuric acid and 2-benzimidazole thiol.

As the carboxylic acid, particularly a monocarboxylic acid is preferablyused. Of them, oleic acid, linoleic acid and linolenic acid arepreferably used.

The intermediate layer can be formed, for example, by laminating, on thecarrier, a nickel layer, a nickel-phosphorus alloy layer or anickel-cobalt alloy layer and a chromium-containing layer in this order.Since the adhesive force between nickel and copper is higher than thatbetween chromium and copper, when an ultra-thin copper layer isdetached, the ultra-thin copper layer can be detached at the interfacebetween the ultra-thin copper layer and the chromium-containing layer.The nickel contained in the intermediate layer is expected to exert abarrier effect, i.e., an effect of preventing diffusion of a coppercomponent from the carrier to the ultra-thin copper layer. The amountdeposited of nickel of the intermediate layer is preferably 100 μg/dm²or more and 40000 μg/dm² or less, more preferably 100 μg/dm² or more and4000 μg/dm² or less, more preferably 100 μg/dm² or more and 2500 μg/dm²or less, and more preferably 100 μg/dm² or more and less than 1000μg/dm². The amount deposited of chromium of the intermediate layer ispreferably 5 μg/dm² or more and 100 μg/dm² or less. In the case wherethe intermediate layer is provided only one of the surfaces of acarrier, a rustproofing layer such as a Ni plated layer is preferablyprovided on the opposite surface of the carrier. The chromium layer ofthe intermediate layer can be formed by chromium plating and treatmentwith a chromate.

If the thickness of the intermediate layer is extremely large, Sz, Saand Sku and surface area ratio A/B of the ultra-thin copper layer aftersurface treatment may be affected by the thickness of the intermediatelayer. The thickness of the intermediate layer on the surface of thesurface treated layer of the ultra-thin copper layer is preferably 1 to1000 nm, preferably 1 to 500 nm, preferably 2 to 200 nm, preferably 2 to100 nm and more preferably 3 to 60 nm. Note that the intermediate layermay be provided to both surfaces of the carrier.

Ultra-Thin Copper Layer

The ultra-thin copper layer is provided on the intermediate layer.Another layer may be provided between the intermediate layer and theultra-thin copper layer. The ultra-thin copper layer which has a carrieris a copper heat dissipation material according to one of theembodiments of the present invention. The thickness of the ultra-thincopper layer, although it is not particularly limited, is generallylower than the thickness of the carrier, for example, 12 μm or less,typically 0.5 to 12 μm and more typically 1.5 to 5 μm. Before anultra-thin copper layer is provided on the intermediate layer, in orderto reduce the number of pinholes in the ultra-thin copper layer, strikeplating by e.g., a copper-phosphorus alloy may be applied. As the strikeplating liquid, for example, a copper pyrophosphate plating liquid maybe mentioned. Note that the ultra-thin copper layer may be provided onboth surfaces of the carrier.

Furthermore, the ultra-thin copper layer of the invention may be anultra-thin copper layer formed in the following conditions. This is forcontrolling Sz, Sa and Sku and surface area ratio A/B of the ultra-thincopper layer surface, when an alloy layer as mentioned above is providedon the surface of the ultra-thin copper layer opposite to the surface incontact with the intermediate layer, in order to control Sz, Sa and Skuand surface area ratio A/B of the alloy layer surface to fall within thescope of the present invention.

Electrolyte Composition

Copper: 80 to 120 g/L

Sulfuric acid: 80 to 120 g/L

Chlorine: 30 to 100 ppm

Leveling agent 1 (bis(3-sulfopropyl)disulfide): 10 to 30 ppm

Leveling agent 2 (amine compound): 10 to 30 ppm

As the above amine compound, an amine compound represented by thefollowing chemical formula can be used.

(where R₁ and R₂ each are selected from the group consisting of ahydroxyalkyl group, an ether group, an aryl group, anaromatic-substituted alkyl group, an unsaturated hydrocarbon group andan alkyl group)

Manufacturing Conditions

Current density: 70 to 100 A/dm²

Electrolyte temperature: 50 to 65° C.

Electrolyte line speed: 1.5 to 5 m/sec

Electrolysis time: 0.5 to 10 minutes (controlled in accordance with thethickness of copper to be precipitated and current density)

Resin Layer

The copper heat dissipation material of the invention may have a resinlayer on one or both surfaces. The surface of the copper heatdissipation material on which the resin layer is to be provided may be atreated surface. The resin layer may be an insulating resin layer. Notethat if a roughening treatment is applied and thereafter surfacetreatments for providing a heat resistant layer, a rustproofing layerand a weather-resistant layer, are applied, the “treated surface” in thecopper heat dissipation material of the invention refers to the surfaceto which the treatments are applied. If the copper heat dissipationmaterial is an ultra-thin copper layer of a carrier-attached copper foiland if a roughening treatment is applied and thereafter surfacetreatments for providing a heat resistant layer, a rustproofing layerand a weather-resistant layer are applied thereto, the “treated surface”refers to the surface of the ultra-thin copper layer to which thetreatments are applied.

The resin layer may be an adhesive layer and may be an insulating resinlayer in a semi-cured state (B-stage), serving as an adhesive. Thesemi-cured state (B-stage) include a state where the surface thereof isnot sticky if touched by a finger; the insulating resin layers of thisstate can be laminated and stored; and a curing reaction proceeds if aheating treatment is further applied.

The resin layer may be formed of a bonding resin, i.e., an adhesive, oran insulating resin layer in a semi-cured state (B-stage), serving as anadhesive. The semi-cured state (B-stage) include a state where thesurface thereof is not sticky if touched by a finger; the insulatingresin layers of this state can be laminated and stored; and a curingreaction proceeds if a heating treatment is further applied.

The resin layer may contain a thermosetting resin or may be formed of athermoplastic resin. The resin layer may contain a thermoplastic resin.The resin layer may contain e.g., a resin known in the art, a resincuring agent, a compound, a curing accelerator, a dielectric substance,a reaction catalyst, a crosslinking agent, a polymer, a prepreg and askeletal material. Furthermore, the resin layer may be formed of thesubstances (resins, resin curing agents, compounds, curing accelerator,a dielectric substance, reaction catalyst, crosslinking agent, apolymer, a prepreg and a skeletal material) described, for example ininternational Publication No. WO2008/004399, International PublicationNo. WO2008/053878, International Publication No. WO2009/084533, JapanesePatent Laid-Open No. 11-5828, Japanese Patent Laid-Open No. 11-140281,Japanese Patent No. 3184485, International Publication No. WO97/02728,Japanese Patent No. 3676375, Japanese Patent Laid-Open No. 2000-43188,Japanese Patent No. 361.2594, Japanese Patent Laid-Open No. 2002-179772,Japanese Patent Laid-Open No. 2002-359444, Japanese Patent Laid-Open No.2003-304068, Japanese Patent No. 3992225, Japanese Patent Laid-Open No.2003-249739, Japanese Patent No. 4136509, Japanese Patent Laid-Open No.2004-82687, Japanese Patent No. 4025177, Japanese Patent Laid-Open No.2004-349654, Japanese Patent No. 4286060, Japanese Patent Laid-Open No.2005-262506, Japanese Patent No. 4570070, Japanese Patent Laid-Open No.2005-53218, Japanese Patent No. 3949676, Japanese Patent No. 4178415,International Publication No. WO2004/005588, Japanese Patent Laid-OpenNo. 2006-257153, Japanese Patent Laid-Open No. 2007-326923, JapanesePatent Laid-Open No. 2008-111169, Japanese Patent No. 5024930,International Publication No. WO2006/028207, Japanese Patent No.4828427, Japanese Patent Laid-Open No. 2009-67029, InternationalPublication No. WO2006/134868, Japanese Patent No. 5046927, JapanesePatent Laid-Open No. 2009-173017, International Publication No.WO2007/105635, Japanese Patent No. 5180815, International PublicationNo. WO2008/114858, International Publication No. WO2009/008471, JapanesePatent Laid-Open No. 2011-14727, International Publication No.WO2009/001850, International Publication No. WO2009/145179,International Publication No. WO2011/068157 and Japanese PatentLaid-Open No. 2013-19056; by using a method for forming a resin layerand/or a forming apparatus.

The type of resin forming the resin layer is not particularly limitedand preferably a resin containing at least one selected from the groupconsisting of an epoxy resin, a polyimide resin, a polyfunctionalcyanate compound, a maleimide compound, a polymaleimide compound, amaleimide resin, an aromatic maleimide resin, a polyvinyl acetal resin,a urethane resin, polyether sulfone, a polyether sulfone resin, anaromatic polyamide resin, an aromatic polyamide resin polymer, a rubberresin, a polyamine, an aromatic polyamine, a polyamide-imide resin, arubber modified epoxy resin, a phenoxy resin, carboxyl group-modifiedacrylonitrile-butadiene resin, a polyphenylene oxide, a bismaleimidetriazine resin, a thermosetting polyphenylene oxide resin, a cyanateresin, an anhydride of a carboxylic acid, an anhydride of a polybasiccarboxylic acid, a linear polymer having a crosslinkable functionalgroup, a polyphenylene ether resin, 2,2-bis(4-cyanatophenyl)propane, aphosphorus-containing phenol compound, manganese naphthenate,2,2-bis(4-glycidylphenyl)propane, a polyphenylene ether-cyanate resin, asiloxane-modified polyamide-imide resin, a cyano ester resin, aphosphazene resin, a rubber-modified polyamide-imide resin, isoprene, ahydrogenated polybutadiene, polyvinyl butyral, phenoxy, a polymer epoxy,an aromatic polyamide, a fluorine resin, a bisphenol, a polyimide blockcopolymer resin and a cyano ester resin.

The epoxy resin has two or more epoxy groups in a molecule. Any epoxyresin can be used without problems as long as it can be used as anelectrical/electron material. An epoxy resin obtained by epoxylating acompound having two or more glycidyl groups in a molecule is preferable.As the epoxy resin, a single resin selected from the group consisting ofa bisphenol A type epoxy resin, a bisphenol F type epoxy resin, abisphenol S type epoxy resin, a bisphenol AD type epoxy resin, a Novolaktype epoxy resin, a cresol Novolak type epoxy resin, an alicyclic epoxyresin, a brominated epoxy resin, a phenol Novolak type epoxy resin, anaphthalene type epoxy resins, a brominated bisphenol A type epoxyresin, an o-cresol Novolak type epoxy resin, a rubber-modified bisphenolA type epoxy resin, a glycidyl amine type epoxy resin, triglycidylisocyanurate, a glycidyl amine compound such as a N,N-diglycidylaniline,glycidyl ester compound such as diglycidyl tetrahydrophthalate, aphosphorus-containing epoxy resin, a biphenyl type epoxy resin, abiphenyl Novolak type epoxy resin, a trishydroxyphenylmethane type epoxyresin and a tetraphenyl ethane epoxy resin, may be used, or two or moreresins selected from the aforementioned group are used as a mixture.Alternatively, these epoxy resins can be hydrogenated or halogenated andput in use.

As the phosphorus-containing epoxy resin, a phosphorus-containing epoxyresin known in the art can be used. The phosphorus-containing epoxyresin is preferably an epoxy resin derived from, a compound having twoor more epoxy groups in a molecule such as9,10-dihydro-9-oxa-10-phospha-phenanthrene-10-oxide.

(Case where the Resin Layer Contains a Dielectric Substance (DielectricSubstance Filler))

The resin layer may contain a dielectric substance (dielectric substancefiller).

If a dielectric substance (dielectric substance filler) is added in anyone of the above resin layers or resin compositions, the dielectricsubstance can be used for forming a capacitor layer to enhance theelectric capacitance of the capacitor circuit. As the dielectricsubstance (dielectric substance filler), a powdery dielectric substanceformed of a composite oxide having a perovskite structure such asBaTiO3, SrTiO3, Pb (Zr—Ti)O3 (alias PZT), PbLaTiO3.PbLaZrO (alias PLZT)and SrBi2Ta2O9 (alias SBT), is used.

A dielectric substance (dielectric substance filler) may be a powder. Ifthe dielectric substance (dielectric substance filler) is a powder, thedielectric substance (dielectric substance filler) preferably has aparticle size within the range of 0.01 μm to 3.0 μm and preferably 0.02μm to 2.0 μm. Note that the particle size of the dielectric substance isobtained as follows. An image of a dielectric substance particle isphotographed by a scanning electron microscope (SEM). Then, linear lineswere drawn on the photographic image of a dielectric substance particle.The length of the longest line crossing the dielectric substanceparticle is defined as the diameter of the dielectric substanceparticle. The average of diameters of the dielectric particles in thefield of view is defined as a particles size of the dielectricsubstance.

A resin, a resin composition and/or a compound contained in theaforementioned resin layer are dissolved in a solvent such as methylethyl ketone (MEK), cyclopentanone, dimethylformamide,dimethylacetamide, N-methylpyrrolidone, toluene, methanol, ethanol,propylene glycol monomethyl ether, dimethylformamide, dimethylacetamide,cyclohexanone, ethyl cellosolve, N-methyl-2-pyrrolidone,N,N-dimethylacetamide and N,N-dimethylformamide to obtain a resin liquid(resin vanish). The resin liquid is applied to a roughened surface of acopper heat dissipation material as mentioned above in accordance withe.g., a roll coater method and, if necessary, dried by heating to removethe solvent to obtain B-stage of the resin. In the drying operation, forexample a hot-air drying furnace may be used. The drying temperature maybe 100 to 250° C. and preferably 130 to 200° C. The composition of theresin layer is dissolved in a solvent to obtain a resin liquidcontaining a resin solid substance of 3 wt % to 70 wt %, preferably, 3wt % to 60 wt %, preferably 10 wt % to 40 wt % and more preferably 25 wt% to 40 wt %. Note that using a solvent mixture of methyl ethyl ketoneand cyclopentanone in dissolving is most preferable from an environmentpoint of view, at present. Note that a solvent having a boiling pointwithin the range of 50° C. to 200° C. is preferable used.

The resin layer is preferably a semi-cured resin film having a resinflow, which is measured in accordance with MIL-P-13949G of the MILstandard, within the range of 5% to 35%.

In the specification, the resin flow is obtained as follows. Inaccordance with the MIL standard (MIL-P-13949G), four 10 cm-squaresamples are taken from a resin-attached copper heat dissipation materialhaving a resin thickness of 55 μm. The four samples are laminated andbonded at a press temperature of 171° C., a press pressure of 14kgf/cm2, for a press time of 10 minutes. At that time, the weight ofresin flowing out is measured and the measurement results aresubstituted in Expression 2 to obtain a value of resin flow.

$\begin{matrix}{{{Resin}{\mspace{11mu}\;}{flow}\mspace{14mu}(\%)} = {\frac{{Weight}\mspace{14mu}{of}\mspace{14mu}{resin}{\mspace{11mu}\;}{flowing}\mspace{14mu}{out}}{\left( {{Laminate}\mspace{14mu}{weight}} \right) - \left( {{Copper}\mspace{14mu}{foil}{\mspace{11mu}\;}{weight}} \right)} \times 100}} & {{Expression}\mspace{14mu} 2}\end{matrix}$

The copper heat dissipation material having the resin layer(resin-attached copper heat dissipation material) is used in thefollowing manner. After the resin layer is laminated on a substrate, theentire construct is subjected to thermocompression to cure the resinlayer. If the copper heat dissipation material is an ultra-thin copperlayer of a carrier-attached copper foil, the carrier is detached toexpose the ultra-thin copper layer (naturally, the surface of theultra-thin copper layer on the side near the intermediate layer isexposed). A predetermined wiring pattern is formed on the surface ofcopper heat dissipation material opposite to the surface to which aroughening treatment is applied.

If the resin-attached copper heat dissipation material is used, thenumber of prepregs used during manufacturing of a multilayer printedcircuit board can be reduced. In addition, the thickness of the resinlayer is controlled such that interlayer insulation can be ensured and ametal-clad laminate can be produced even if a prepreg material is notused at all. At this time, if the surface of the substrate isundercoated with an insulating resin, smoothness of the surface can befurther improved.

Note that the case where a prepreg material is not used is economicallyfavorable because the cost for a prepreg material can be saved and thelaminating step is simplified. In addition, the thickness of theresultant multilayer printed circuit board can be reduced by thethickness of the prepreg material. As a result, an ultra-thin multilayerprinted wiring board (a thickness of a single layer: 100 μm or less) isadvantageously produced.

The thickness of the resin layer is preferably 0.1 to 120 μm.

If the thickness of the resin layer is lower than 0.1 μm, adhesive forcereduces. If such a resin-attached copper heat dissipation material islaminated on a substrate having an interlayer material withoutinterposing a prepreg material, it is sometimes difficult to ensureinterlayer insulation with the circuit of the interlayer material. Incontrast, if the thickness of the resin layer is larger than 120 μm, itbecomes difficult to form a resin layer having a desired thickness in asingle coating step and an extra material cost and a number of steps arerequired. This case may be economically disadvantageous.

Note that if the copper heat dissipation material having a resin layeris used for forming the ultra-thin multilayer printed wiring board, theresin layer having a thickness of 0.1 μm to 5 μm, more preferably 0.5 μmto 5 μm and more preferably 1 μm to 5 μm is preferably used for reducingthe thickness of the multilayer printed wiring board.

Now, several manufacturing processes for a printed-wiring board using acarrier-attached copper foil according to the present invention will bedescribed below.

In an embodiment of the method of manufacturing a printed wiring boardaccording to the present invention, the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate;

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated such that an ultra-thin copper layer faces the insulatingsubstrate), to form a metal-clad laminate; and thereafter

a step of forming a circuit by any one of a semi-additive method, amodified semi-additive method, a partly additive method and asubtractive method. The insulating substrate may have an inner layercircuit.

In the present invention, the semi-additive method refers to a method offorming a conductive pattern by applying non-electrolytic plating ontoan insulating substrate or a metal foil seed layer to form a thinplating layer, forming a pattern, and thereafter applying electroplatingand etching.

Accordingly, in the embodiment of the method of manufacturing a printedwiring board according to the present invention using the semi-additivemethod, the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated);

a step of completely removing an ultra-thin copper layer exposed bydetaching the carrier by e.g., an etching method using a corrosivesolution such as an acid, or a plasma method;

a step of forming through-holes or/and blind vias in the resin exposedby removing the ultra-thin copper layer by etching,

a step of applying a desmear treatment to a region containing thethrough-holes or/and blind vias,

a step of providing an non-electrolytic plating layer on the regioncontaining the resin, the through-holes or/and blind vias,

a step of forming a plating resist on the non-electrolytic platinglayer,

a step of applying light to the plating resist to remove the platingresist of a region in which the circuit is to be formed,

a step of forming an electrolytic plating layer on the region in whichthe circuit is to be formed and the plating resist has been removed

a step of removing the plating resist; and

a step of removing the non-electrolytic plating layer present in theregion except the region in which the circuit is to be formed, by e.g.,flash etching.

In another embodiment of the method of manufacturing a printed wiringboard according to the present invention using the semi-additive method,the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated);

a step of completely removing an ultra-thin copper layer exposed bydetaching the carrier by an etching method using a corrosive solutionsuch as an acid, or a plasma method;

a step of forming a non-electrolytic plating layer on the surface of theresin exposed by removing the ultra-thin copper layer by etching,

a step of forming a plating resist on the non-electrolytic platinglayer,

a step of applying light to the plating resist, and thereafter removingthe plating resist of a region in which the circuit is to be formed,

a step of forming an electrolytic plating layer on the region in whichthe circuit is to be formed and the plating resist has been removed;

a step of removing the plating resist; and

a step of removing the non-electrolytic plating layer and the ultra-thincopper layer present in the region except the region in which thecircuit is to be formed, by e.g., flash etching.

In the present invention, the modified semi-additive method refers to amethod of forming a circuit on an insulating layer by laminating a metalfoil on an insulating layer, protecting a non-circuit forming portionwith a plating resist, thickening a circuit forming portion with copperby electrolytic plating, removing the resist and removing the metal foilof the region except the circuit forming portion by (flash) etching.

Accordingly, in the embodiment of the method of manufacturing a printedwiring board according to the present invention using the modifiedsemi-additive method, the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated);

a step of forming through-holes or/and blind vias in the ultra-thincopper layer exposed by detaching the carrier and the insulatingsubstrate,

a step of applying a desmear treatment to a region containing thethrough-holes or/and blind vias,

a step of providing an non-electrolytic plating layer on the regioncontaining the through-holes or/and blind vias,

a step of forming a plating resist on the surface of the ultra-thincopper layer exposed by detaching the carrier,

a step of forming a circuit by electro plating (after the plating resistis formed),

a step of removing the plating resist; and

a step of removing the ultra-thin copper layer exposed by removing theplating resist, by flash etching.

The step of forming a circuit on the resin layer may be a step ofbonding another carrier-attached copper foil to the resin layer from theside of the ultra-thin copper layer and forming the circuit using thecarrier-attached copper foil attached to the resin layer. Thecarrier-attached copper foil to be bonded to the resin layer may be thecarrier-attached copper foil of the invention. The step of forming acircuit on the resin layer may be performed by any one of asemi-additive method, a subtractive method, partly additive step and amodified semi-additive method. The carrier-attached copper foil forminga circuit on the surface may have a substrate or a resin layer on thesurface of the carrier of the carrier-attached copper foil.

In another embodiment of the method of manufacturing a printed wiringboard according to the present invention using the modifiedsemi-additive method, the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated),

a step of forming a plating resist on the ultra-thin copper layerexposed by detaching the carrier,

a step of applying light to the plating resist to remove the platingresist in the region in which a circuit is to be formed,

a step of forming an electrolytic plating layer on the region in whichthe circuit is to be formed and the plating resist has been removed,

a step of removing the plating resist; and

a step of removing the non-electrolytic plating layer and the ultra-thincopper layer in the region except the region in which the circuit is tobe formed, by e.g., flash etching.

In the present invention, the partly additive method refers to a methodof manufacturing a printed-wiring board, which includes providing acatalyst nucleus on a substrate having a conductor layer and, ifnecessary, having holes for through-holes and via holes, forming aconductor circuit by etching, providing a solder resist or a platingresist, as needed, and thickening the conductor circuit, e.g.,through-hole and via holes, by non-electrolytic plating.

Accordingly, in the embodiment of the method of manufacturing a printedwiring board according to the present invention using the partlyadditive method, the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated),

a step of forming through-holes or/and blind vias in the ultra-thincopper layer exposed by detaching the carrier and the insulatingsubstrate,

a step of applying a desmear treatment to the region containing thethrough-hole or/and blind vias,

a step of providing a catalyst nucleus to the region containing thethrough-hole or/and blind vias,

a step of providing an etching resist to the ultra-thin copper layersurface exposed by detaching the carrier,

a step of forming a circuit pattern by applying light to the etchingresist,

a step of forming a circuit by removing the ultra-thin copper layer andthe catalyst nucleus by e.g., an etching method using a corrosivesolution such as an acid, or a plasma method,

a step of removing the etching resist,

a step of forming a solder resist or a plating resist on the surface ofthe insulating substrate exposed by removing the ultra-thin copper layerand the catalyst nucleus by e.g., an etching method using a corrosivesolution such as an acid, or a plasma method; and

a step of providing a non-electrolytic plating layer in the region inwhich neither the solder resist nor plating resist is provided.

In the present invention, the subtractive method refers to a method offorming a conductive pattern by selectively removing an unwanted part inthe copper foil on a metal-clad laminate by e.g., etching.

Accordingly, in the embodiment of the method of manufacturing a printedwiring board according to the present invention using the subtractivemethod, the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated),

a step of forming through-holes or/and blind vias in the ultra-thincopper layer exposed by detaching the carrier and insulating substrate,

a step of applying a desmear treatment to the region containing thethrough-hole or/and blind vias,

a step of providing an non-electrolytic plating layer in the regioncontaining the through-hole or/and blind vias,

a step of providing an electrolytic plating layer on the surface of thenon-electrolytic plating layer,

a step of providing an etching resist on the surface of the electrolyticplating layer or/and the ultra-thin copper layer,

a step of forming a circuit pattern by applying light to the etchingresist,

a step of forming a circuit by removing the ultra-thin copper layer,non-electrolytic plating layer and electrolytic plating layer by e.g.,an etching method using a corrosive solution such as an acid, or aplasma method; and

a step of removing the etching resist.

In another embodiment of the method of manufacturing a printed wiringboard according to the present invention using the subtractive method,the method of the invention includes

a step of preparing a carrier-attached copper foil according to thepresent invention and an insulating substrate,

a step of laminating the carrier-attached copper foil and the insulatingsubstrate,

a step of detaching the carrier from the carrier-attached copper foil(after the carrier-attached copper foil and the insulating substrate arelaminated),

a step of forming through-holes or/and blind vias in the ultra-thincopper layer exposed by detaching the carrier and insulating substrate

a step of applying a desmear treatment to the region containing thethrough-hole or/and blind vias,

a step of providing an non-electrolytic plating layer on the regioncontaining the through-hole or/and blind vias,

a step of forming a mask on the surface of the non-electrolytic platinglayer,

a step of forming an electrolytic plating layer on the surface of thenon-electrolytic plating layer in which no mask is formed,

a step of forming an etching resist on the surface of the electrolyticplating layer or/and the ultra-thin copper layer,

a step of forming a circuit pattern by applying light to the etchingresist,

a step of forming a circuit by removing the ultra-thin copper layer andthe non-electrolytic plating layer by e.g., an etching method using acorrosive solution such as an acid, or a plasma method; and

a step of removing the etching resist.

The step of forming through-holes or/and blind vias and the followingdesmear step may not be performed.

Now, the method of manufacturing a printed wiring board using thecarrier-attached copper foil of the invention will be more specificallydescribed below. Note that the method will be described herein withreference to a carrier-attached copper foil having an ultra-thin copperlayer having a roughened layer formed; however, the invention is notlimited thereto. Even if a carrier-attached copper foil having anultra-thin copper layer having no roughened layer is used, the followingmethod of manufacturing a printed wiring board will be similarlyperformed.

First, a carrier-attached copper foil (first layer) having an ultra-thincopper layer having a roughened layer formed on the surface is prepared.

Next, a resist is applied onto the roughened layer on the ultra-thincopper layer and subjected to a light exposure and development operationto etch the resist into a predetermined shape.

Next, plating for a circuit is formed and thereafter the resist isremoved to form a circuit plating having a predetermined shape.

Next, an embedding resin is provided on the ultra-thin copper layer soas to cover the circuit plating (so as to bury the circuit plating) andsubsequently another carrier-attached copper foil (second layer) isbonded from the side of the ultra-thin copper layer.

Next, carrier is removed from the second layer carrier-attached copperfoil.

Next, holes are formed by applying laser at the predetermined positionsof the resin layer and the circuit plating is exposed to light to formblind vias.

Next, blind vias are embedded with copper to form via fill.

Next, circuit plating is formed on the via fill, as described above.

Next, the carrier is removed from the firth carrier-attached copperfoil.

Next, the ultra-thin copper layer of both surfaces are removed by flashetching to expose the surface of the circuit plating within the resinlayer.

Next, bumps are formed on the circuit plating within the resin layer anda copper pillar is formed on the solder. In this manner, aprinted-wiring board using the carrier-attached copper foil of theinvention is prepared.

As the above another carrier-attached copper foil (second layer), thecarrier-attached copper foil of the invention, a conventionalcarrier-attached copper foil or a general copper foil may be used. Onthe circuit on the second layer, a single-layer circuit or plural-layercircuits may be formed. These circuits may be formed by any one of asemi-additive method, a subtractive method, a partly additive step and amodified semi-additive method.

Note that as the embedding resin (resin), a resin known in the art and aprepreg can be used. For example, BT (bismaleimide triazine) resin and aprepreg, which is glass cloth impregnated with a BT resin, ABF film andABF manufactured by Ajinomoto Fine-Techno Co., Inc. can be used. As theembedding resin (resin), the resin layer and/or resin and/or prepregdescribed in the specification can be used.

Furthermore, the carrier-attached copper foil used as the first layermay have a substrate or a resin layer on a surface. The presence of thesubstrate or resin layer is advantageous since the carrier-attachedcopper foil used as the first layer is supported and wrinkle is rarelyformed, with the result that productivity is improved. Note that as thesubstrate or resin layer, any substrate or resin layer may be used aslong as it has an effect of supporting the carrier-attached copper foilused as the first layer. Example of the substrate or resin layer thatcan be used herein include a carrier, a prepreg and a resin layer asdescribed in the specification as the carrier or the resin layer; acarrier, a prepreg, a resin layer, a metal plate, a metal foil, a plateof an inorganic compound, a foil of an inorganic compound, a board of anorganic compound and a foil of an organic compound known in the art.

A laminate can be formed by bonding the copper heat dissipation materialof the invention to a resin substrate from the side of the surfacetreated layer or the side opposite to the surface treated layer. Theresin substrate is not particularly limited as long as it has propertiesapplicable to e.g., a printed-wiring board. Examples of the resinsubstrate that can be used for a rigid PWB include a paper based phenolresin, a paper based epoxy resin, a synthetic fiber cloth based epoxyresin, a cloth impregnated with a fluorine resin, a glass cloth/papercomposite based epoxy resin, a glass cloth/non-woven glass clothcomposite based epoxy resin and a glass cloth based epoxy resin.Examples of the resin substrate that can be used for a flexible printedcircuit board (FPC) include a polyester film and a polyimide film, aliquid crystal polymer (LCP) film, a fluorine resin and a fluorineresin/polyimide composite. Note that since the dielectric loss of theliquid crystal polymer (LCP) is low, a liquid crystal polymer (LCP) filmis preferably used in a printed-wiring board for a high-frequencycircuit.

The copper heat dissipation material can be bonded to a substrate for arigid PWB in accordance with the following method. First, a prepreg isprepared by impregnating a substrate such as glass cloth with a resinand hardening the resin up to a semi-cured state. Then, a copper foil islaminated on the prepreg and heated/pressured.

In the case of an FPC, a laminate can be formed by laminating andbonding a copper foil to a substrate such as a liquid crystal polymerand a polyimide film, with an adhesive or without an adhesive interposedtherein under a high temperature and a high pressure or by applying apolyimide precursor on the substrate followed by drying and curing.

The laminate of the invention can be used in various types ofprinted-wiring boards (PWB), which are not particularly limited. Inconsideration of the number of conductive pattern layers, the laminateis applicable, for example, to a one-sided PWB, a two-sided PWB and amultilayered PWB (three layers or more). In contrast, in considerationof the types of insulating substrate materials, the laminate isapplicable to rigid PWB, flexible PWB (FPC) and rigid/flex PWB.

The copper heat dissipation material of the invention or thecarrier-attached copper foil of the invention may be laminated on aresin substrate or substrate (which may be formed of a metal material,an inorganic material, an organic material, a ceramic) such that asurface treated layer side or the opposite side thereof faces to thesubstrate, or laminating on a chassis, a metal processed member, anelectronic component, an electronic device, a liquid crystal panel or adisplay to form a laminate.

The laminate may have a pressure-sensitive adhesive layer or an adhesivelayer between the copper heat dissipation material of the invention orthe carrier-attached copper foil of the invention and the resinsubstrate or the substrate. The pressure-sensitive adhesive layer may bea layer using a conductive adhesive or a layer using a conductiveacrylic adhesive. The resin substrate or substrate may be a separator.The separator refers to a resin substrate or a substrate, which enablesthe pressure-sensitive adhesive layer or adhesive layer and the copperheat dissipation material of the invention or the carrier-attachedcopper foil of the invention to be separated from the laminate. Thecopper heat dissipation material of the invention or thecarrier-attached copper foil of the invention and the resin substrate orthe substrate may be detachable.

If the laminate is a laminate having a pressure-sensitive adhesive layeror an adhesive layer between the copper heat dissipation material of theinvention or the carrier-attached copper foil of the invention and theresin substrate and the substrate, the copper heat dissipation materialof the invention or the carrier-attached copper foil of the inventionand the resin substrate or the substrate may be detachable.

In the above case, when the copper heat dissipation material of theinvention or the carrier-attached copper foil of the invention isdetached from the resin substrate or the substrate, thepressure-sensitive adhesive layer or adhesive layer is exposed on thesurface of the copper heat dissipation material of the invention or thecarrier-attached copper foil of the invention. Because of this, thecopper heat dissipation material of the invention or thecarrier-attached copper foil of the invention, from which the resinsubstrate or substrate is detached, can be laminated on another object.The laminate may have the copper heat dissipation material of theinvention or the carrier-attached copper foil of the invention on bothsides of the resin substrate or the substrate.

Note that, as the pressure-sensitive adhesive layer and adhesive layer,e.g., a pressure-sensitive adhesive and an adhesive known in the art,the resin layer described in the specification and a resin that can beused in the resin layer described in the specification, can be used.

A printed-wiring board and a copper clad laminate board can bemanufactured by using the copper heat dissipation material of theinvention. The printed-wiring board manufactured by using the coppermaterial of the present invention can be used in electronic devices. Thecopper material of the present invention can be used as e.g., asupporting substrate to be used in manufacturing a negative electrodecurrent collector for a secondary battery, a secondary battery and acoreless multilayer printed wiring board.

EXAMPLES Examples 1 to 11, 13 to 18, Comparative Examples 1 to 8

As Examples 1 to 11, 13 to 18 and Comparative Examples 1 to 8, varioustypes of copper substrates having the thicknesses described in Tables 1to 4 were prepared. Next, on each of the copper substrates, alloy layerswere formed; more specifically, alloy layers (1) to (3) shown in Tables1 to 4, were formed in this order.

Example 12

As the substrate of Example 12, the following carrier-attached copperfoil was prepared. First, an electrolytic copper foil, i.e., JTC foil(manufactured by JX Mining & Metals Corporation) having a thickness of18 μm was prepared as a carrier. Then, an intermediate layer was formedon the glossy surface of the carrier in the following conditions and anultra-thin copper layer was formed on the intermediate layer.

Intermediate Layer

(1) Ni Layer (Ni Plating)

The carrier was electroplated on a roll-to-roll continuous plating linein the following conditions to form a Ni layer in an amount deposited of1000 μg/dm². The plating conditions are more specifically as follows.

Nickel sulfate: 270 to 280 g/L

Nickel chloride: 35 to 45 g/L

Nickel acetate: 10 to 20 g/L

Boric acid: 30 to 40 g/L

Gloss agent: e.g., saccharin, butynediol

Sodium dodecyl sulfate: 55 to 75 ppm

pH: 4 to 6

Bath temperature: 55 to 65° C.

Current density: 10 A/dm²

(2) Cr Layer (Electrolytic Chromate Treatment)

Next, the surface of the Ni layer formed in (1) was washed with waterand an acid. Subsequently, on the Ni layer, a Cr layer (amountdeposited: 11 μg/dm²) was formed in accordance with an electrolyticchromate treatment on the roll-to-roll continuous plating line in thefollowing conditions.

Potassium dichromate: 1 to 10 g/L

pH: 7 to 10

Liquid temperature: 40 to 60° C.

Current density: 2 A/dm²

Ultra-Thin Copper Layer

Next, the surface of the Cr layer formed in (2) was washed with waterand an acid. Subsequently, on the Cr layer, an ultra-thin copper layerof 5 μm in thickness was formed in accordance with electrical plating onthe roll-to-roll continuous plating line in the following conditions. Inthis manner, a carrier-attached ultra-thin copper foil was prepared.

Copper concentration: 90 to 110 g/L

Sulfuric acid concentration: 90 to 110 g/L

Chloride ion concentration: 50 to 90 ppm

Leveling agent 1 (bis(3-sulfopropyl)disulfide): 10 to 30 ppm

Leveling agent 2 (amine compound): 10 to 30 ppm

Note that as the leveling agent 2, the following amine compound wasused.

(where R₁ and R₂ each are selected from the group consisting of ahydroxyalkyl group, an ether group, an aryl group, anaromatic-substituted alkyl group, an unsaturated hydrocarbon group andan alkyl group).

Electrolyte temperature: 50 to 80° C.

Current density: 100 A/dm²

Electrolyte line speed: 1.5 to 5 m/sec

Surface Sz, Sa and Sku

Sz, Sa and Sku of the surface of the copper heat dissipation materialwere measured by a laser microscope OLS4000 (LEXT OLS 4000) manufacturedby Olympus Corporation in accordance with ISO25178. An area of about 200μm×200 μm (specifically 40106 μm²) was measured by use of a 50×objective lens of the laser microscope and Sz, Sa and Sku werecomputationally obtained. Note that, in the laser microscopemeasurement, if the measuring surface is not flat, i.e., a curvedsurface, plane correction was applied to the measurement results andthen Sz, Sa and Sku were computationally obtained. Note that theenvironment temperature when Sz, Sa and Sku were measured by the lasermicroscope was set at 23 to 25° C.

Surface Area Ratio A/B

The surface area of a copper heat dissipation material surface wasmeasured by a laser microscope OLS4000 (LEXT OLS 4000) manufactured byOlympus Corporation in accordance with ISO25178. Based on themeasurement results, a surface area ratio A/B was calculated. An area ofabout 200 μm×200 μm (specifically 40106 μm²) was measured by use of a50× objective lens of the laser microscope. Note that the environmenttemperature when three-dimensional surface area A was measured by thelaser microscope was set at 23 to 25° C.

Color Difference

The color difference of the surface of a copper heat dissipationmaterial was measured using a color difference meter, MiniScan XE Plusmanufactured by HunterLab, in accordance with JISZ8730 and based on theobject color of a white plate (when D65 is used as a light source and afield of view is set to have a viewing angle of 10°, the tristimulusvalues of the X₁₀Y₁₀Z₁₀ color system (JIS Z8701 1999) of the white plateare X₁₀=80.7, Y₁₀=85.6, Z₁₀=91.5 and the object color of the white plateof the L*a*b* color system is expressed by L*=94.14, a*=−0.90, b*=0.24).Note that in the aforementioned color-difference meter, the colordifference is corrected, provided that the measured value of the colordifference of the white plate is determined as ΔE*ab=0, the measurementvalue of color difference measured by covering a measurement hole with ablack bag (light trap) was determined as ΔE*ab=94.14. Color differenceΔE*ab of the white plate is defined as zero and Color difference ΔE*abof black is defined as 94.14. Note that the color difference ΔE*ab basedon JIS Z8730 of a small region such as a copper circuit surface can bemeasured by a measurement apparatus known in the art, for Example, amicro-surface spectral color difference meter (model: e.g., VSS400)manufactured by Nippon Denshoku Industries Co., Ltd. and manufactured bya micro-surface spectrophotometer (model: e.g., SC-50μ) manufactured bySuga Test Instruments Co., Ltd.

Dusting

Dusting was evaluated by bonding a transparent mending tape on asurface, removing the tape and observing discoloration of the tape bythe particles attached to the adhesive surface of the tape. The casewhere the color of the tape was not changed is represented by adouble-circle, the case where the color of the tape was gray by a circleand the case where the color of the tape is black by X-mark.

Radiation Factor

The reflectance spectrum of the surface of a copper heat dissipationmaterial was measured by Fourier Transform Infrared Spectroscopy (FT-IR)in the following conditions and a radiation factor was computationallyobtained.

(1) Evaluation of Heat Dissipation

At the center of the surface of a substrate (Mg alloy die-casting),having a size of length d2×width w2×thickness h2=50 mm×100 mm×0.2 mm, asshown in FIG. 1, an exothermic body (an exothermic body formed ofheating-wire bonded with a resin, corresponding to IC CHIP) having asize of length d1×width w1×thickness h1=5 mm×5 mm×1 mm, was placed.Next, on the surface of the substrate opposite to the surface having theexothermic body placed thereon, an adhesive layer (length d3×widthw3×thickness h3=50 mm×100 mm×0.03 mm) was provided and further a copperheat dissipation material (length d4×width w4×thickness h4=50 mm×100mm×the thickness of a copper substrate described in Table) according toeach of Examples and Comparative Examples was laminated to the adhesivelayer from the side of the surface opposite to the surface having thealloy layer formed thereon. A thermocouple was provided at the center ofthe exothermic body and at the site corresponding to the center of theexothermic body on the surface of the copper heat dissipation materialopposite to the surface having the adhesive layer laminated thereon.FIG. 1 (A) shows a schematic view of the copper heat dissipationmaterial (hereinafter referred to as “sample material”) as viewed fromthe top. FIG. 1 (B) shows a schematic cross-sectional view of the samplematerial.

Next, to the exothermic body, current was supplied so as to obtain acalorific value of 0.5 W. The current supply was continued until thetemperature of the top center portion of the exothermic body reached aconstant value. Herein, if the temperature of the top center portion ofthe exothermic body did not change for 10 minutes, it was determinedthat the temperature of the top center portion reached the constantvalue. Note that the external environment temperature was set at 20° C.After the temperature of the top center portion of the exothermic bodyreached the constant value, the copper heat dissipation material wasmaintained for 30 minutes in the same state, and then the temperaturedisplayed by the thermocouple provided on the above copper heatdissipation material was checked. It was evaluated that if thetemperature displayed by the thermocouple is lower, the heat dissipationis better. Note that the temperature of the site corresponding to thecenter of the exothermic body on the surface of the copper heatdissipation material opposite to the surface having the adhesive layerlaminated thereon is found to be highest in the copper heat dissipationboard.

(2) Reflectometry

Reflectance of the above sample material to light was measured in thefollowing conditions. Measurement was performed within the measuringsurface of the sample material by turning the measurement direction 90°,twice.

Measurement apparatus: IFS-66v (FT-IR, vacuum optical system,manufactured by Bruker)

Light source: Grover (SiC)

Detector: MCT (HgCdTe)

Beam splitter: Ge/KBr

Measurement conditions: resolution=4 cm⁻¹

Cumulative number of times=512 times

Zero filling=2 times

Apodization=triangle

Measurement area=5000 to 715 cm⁻¹ (wavelength of light: 2 to 14 μm)

Measurement temperature=25° C.

Accessory equipment: transmittance, reflectance measurement integratingsphere

Port diameter=φ10 mm

Repeatability=about ±1%

Reflectometry

Incident angle: 10 degrees

Reference sample: diffuse gold (Infragold-LF Assembly)

Specular cup (specular component removal device), not attached.

(3) Re: Radiation Factor

Incident light on the surface of a sample material is reflected,transmitted or otherwise, absorbed by the interior. Absorptivity (α)(=radiation factor (ε)), reflectance (r) and transmittance (t) satisfythe following expression.ε+r+t=1  (A)

The radiation factor (ε) can be obtained from reflectance andtransmittance as shown in the following expression.ε=1−r−t  (B)

In the case where a sample material is so opaque or thick thattransmittance is ignorable, t=0 and thus radiation factor is determinedonly by reflectance.ε=1−r  (C)

In the sample material of the invention, since infrared light did nottransmit, Expression (C) is employed and radiation factor of light ofeach wavelength was calculated.

(4) FT-IR Spectrum

Measurement was performed twice. The resultant average value wasregarded as a reflectance spectrum. Note that the reflectance spectrumwas corrected based on the reflectance of diffuse gold (displaywavelength region: 2 to 14 μm).

From the radiant energy distribution of a black object at apredetermined temperature obtained by the Planck expression, the radiantenergy intensity E_(sλ) of the sample material is expressed byE _(sλ)=ε_(λ) ·E _(bλ)where the energy intensity at wavelength λ is represented by E_(bλ); andthe radiation factor of a sample material at wavelength λ is representedby ελ.

In Examples of the invention, radiant energy intensity E_(sλ) of eachsample material (which is obtained by Expression: E_(sλ)=ε_(λ)·E_(bλ))was obtained at 25° C.

Furthermore, the total energy values of a black object and the samplematerial in a predetermined wavelength region were obtained as theintegral values of E_(sλ), E_(bλ) in the wavelength range, the totalradiation factor ε is represented by its ratio (the following ExpressionA). In Examples of the invention, total radiation factor ε of eachsample material at 25° C. and a wavelength region of 2 to 14 μm wascalculated based on the Expression. The obtained total radiation factors was used as a radiation factor of each sample material.ε=∫_(λ=2) ^(λ=14) E _(s) _(λ) dλ/∫ _(λ=2) ^(λ=14) E _(b) _(λ) dλ  (A)

The conditions and test results of each test are shown in Tables 1 to 4.

TABLE 1 Thickness Type Treatment of Formation Formation Formation ofstep for copper of alloy of alloy of alloy copper copper substrate layerlayer layer Color substrate substrate [μm] (1) (2) (3) difference Exam-Tough General 18 None None (Ni—Zn) ΔL −66.4 ple pitch metal Current Δa2.7 1 copper rolling density Δb 2.6 oil film 0.5 A/dm2 ΔE*ab 65.2equivalent Treatment 26000 time 20 seconds Times of treatment 1 timeExam- Tough General 18 None None (Ni—Zn) ΔL −70.0 ple pitch metalCurrent Δa 1.8 2 copper rolling density Δb 2.0 oil film 1.0 A/dm2 ΔE*abequivalent Treatment 26000 time 20 seconds Times of treatment 1 timeExam- Tough General 18 (Ni—Zn) (Ni—Zn) (Ni—Zn) ΔL −82.0 ple pitch metalCurrent Current Current Δa 5.8 3 copper rolling density density densityΔb −5.0 oil film 0.6 A/dm2 0.6 A/dm2 0.6 A/dm2 ΔE*ab 82.2 equivalentTreatment Treatment Treatment 26000 time 10 time 10 time 10 secondsseconds seconds Times of Times of Times of treatment treatment treatment2 2 2 times times times Exam- Tough General 18 (Cu) (Cu) (Ni—Zn) ΔL−72.9 ple pitch metal Current Current Current Δa 2.2 4 copper + rollingdensity density density Δb −3.2 Ag:180 oil film 65 A/dm2 10 A/dm2 0.5A/dm2 ΔE*ab 73.0 ppm equivalent Treatment Treatment Treatment 26000 time0.5 time 5 time 20 seconds seconds seconds Times of Times of Times oftreatment treatment treatment 2 2 1 times times time1 Exam- ToughGeneral 18 (Cu) (Ni—Zn) (Ni—Zn) ΔL −86.7 ple pitch metal Current CurrentCurrent Δa 1.1 5 copper + rolling density density density Δb −1.3 Ag:180oil film 65 A/dm2 0.6 A/dm2 0.6 A/dm2 ΔE*ab 86.7 ppm equivalentTreatment Treatment Treatment 26000 time 0.5 time 10 time 10 secondsseconds seconds Times of Times of Times of treatment treatment treatment2 2 2 times times times Exam- Tough General 12 (Cu) (Cu) (Ni-Zn) ΔL−68.3 ple pitch metal Current Current Current Δa 3.1 6 copper + rollingdensity density density Δb −4.3 Ag:180 oil film 55 A/dm2 10 A/dm2 0.5A/dm2 ΔE*ab 68.6 ppm equivalent Treatment Treatment Treatment 26000 time0.5 time 5 time 20 seconds seconds seconds Times of Times of Times oftreatment treatment treatment 2 2 2 times times times Exam- No- General18 (Cu—Co—Ni—P) (Cu—Co—Ni—P) None ΔL −61.2 ple oxygen metal CurrentCurrent Δa 3.4 7 copper + rolling density density Δb 0.5 Ag:100 oil film35 A/dm2 45 A/dm2 ΔE*ab 61.3 ppm equivalent Treatment Treatment 26000time 0.4 time 0.4 seconds seconds Times of Times of treatment treatment2 2 times times Exam- No- General 18 (Cu) (Cu) (Cu—Co—Ni—P) ΔL −48.8 pleoxygen metal Current Current Current Δa 4.0 8 copper + rolling densitydensity density Δb 1.9 Ag:100 oil film 55 A/dm2 3 A/dm2 27 A/dm2 ΔE*ab49.0 ppm equivalent Treatment Treatment Treatment 26000 time 0.7 time 2time 0.6 seconds seconds seconds Times of Times of Times of treatmenttreatment treatment 2 2 2 times times times Exam- No- General 18(Cu—Co—Ni—P) None None ΔL −52.2 ple oxygen metal Current Δa 2.3 9copper + rolling density Δb 1.7 Ag:100 oil film 35 A/dm2 ΔE*ab 52.3 ppmequivalent Treatment 17000 time 20 seconds Times of treatment 2 timesExam- No- General 35 (Cu) (Cu—Ni—P) (Cu—Ni—P) ΔL −58.7 ple oxygen metalCurrent Current Current Δa 2.9 10 copper + rolling density densitydensity Δb −1.2 Ag:100 oil film 55 A/dm2 40 A/dm2 35 A/dm2 ΔE*ab 58.8ppm equivalent Treatment Treatment Treatment 26000 time 0.5 time 0.4time 0.4 seconds seconds seconds Times of Times of Times of treatmenttreatment treatment 2 2 2 times times times Exam- Electro- 18 (Cu) (Cu)(Ni—Zn) ΔL −77.2 ple lytic Current Current Current Δa 2.1 11 copperdensity density density Δb −4.3 foil 65 A/dm2 10 A/dm2 1.0 A/dm2 ΔE*ab77.3 Treatment Treatment Treatment time 0.5 time 5 time 20 secondsseconds seconds Times of Times of Times of treatment treatment treatment2 2 2 times times times Exam- Carrier- Carrier: 5 (Cu) (Cu) (Ni—Zn) ΔL−77.2 ple attached (Electro- Current Current Current Δa 2.1 12 copperlytic density density density Δb −4.3 foil foil) 65 A/dm2 10 A/dm2 1.0A/dm2 ΔE*ab 77.3 Inter- Treatment Treatment Treatment mediate time 0.5time 5 time 20 layer seconds seconds seconds and Times of Times of Timesof extremely treatment treatment treatment thin 2 2 1 copper times timestimes layer are provided on S surface Maximum surface temperatureSurface roughness Surface Radi- of copper (measured by laser) Surfacearea aton dissipation Sz Sa area ratio factor material [μm] [μm] Sku[μm²] A/B Dusting [-] ° C. Exam- 20.22 0.19 63.27 55464.478 1.38 Double-0.157 57.8 ple circle 1 Exam- 23.10 0.20 34.23 55864.243 1.39 Circle0.166 57.7 ple 2 Exam- 34.80 0.31 15.11 59864.243 1.49 Circle 0.222 57.1ple 3 Exam- 15.92 0.24 9.14 55497.941 1.38 Double- 0.188 57.5 ple circle4 Exam- 18.16 0.26 9.24 55497.941 1.38 Circle 0.190 57.4 ple 5 Exam-13.23 0.20 15.31 54397.941 1.36 Double- 0.206 57.3 ple circle 6 Exam-10.72 0.31 8.47 58857.025 1.47 Circle 0.200 57.3 ple 7 Exam- 23.85 0.4118.03 57424.781 1.43 Double- 0.194 57.4 ple circle 8 Exam- 15.58 0.13110.95 53654.485 1.34 Double- 0.124 58.2 ple circle 9 Exam- 18.76 0.2360.12 54276.257 1.35 Circle 0.151 57.9 ple 10 Exam- 18.57 0.35 8.9156132.735 1.40 Circle 0.200 58.4 ple 11 Exam- 18.62 0.36 8.81 56326.6391.40 Circle 0.200 58.5 ple 12

TABLE 2 Thickness Type Treatment of Formation Formation Formation ofstep for copper of alloy of alloy of alloy copper copper substrate layerlayer layer Color substrate substrate [μm] (1) (2) (3) difference Exam-Copper General 70 (Cu) (Cu) (Ni—W—Zn) ΔL −63.8 ple alloy metal CurrentCurrent Current Δa 3.5 15 (Cu-Sn0.12%) rolling density density densityΔb −2.8 oil film 55 A/dm2 10 A/dm2 1.0 A/dm2 ΔE*ab 64.0 equivalentTreatment Treatment Treatment 26000 time 0.5 time 5 time 20 secondsseconds seconds Times of Times of Times of treatment treatment treatment2 2 2 times times times Exam- Copper General 35 (Cu—Ni—Mo—Fe)(Cu—Ni—Mo—Fe) (Cu—Ni—Mo—Fe) ΔL −79.3 ple alloy metal Current CurrentCurrent Δa 2.1 16 C194 Cu- rolling density density density Δb −1.2Fe2.2%- oil film 30 A/dm2 40 A/dm2 40 A/dm2 ΔE*ab 79.3 P0.03%-equivalent Treatment Treatment Treatment Zn0.15%) 26000 time 0.7 time0.5 time 0.5 seconds seconds seconds Times of Times of Times oftreatment treatment treatment 2 2 2 times times times Exam- CopperGeneral 35 (Cu—Ni—Mo—Fe) (Cu—Ni—Mo—Fe) (Cu—Ni—Mo—Fe) ΔL −81.7 ple alloymetal Current Current Current Δa 2.0 17 C194 Cu- rolling density densitydensity Δb −1.0 Fe2.2%- oil film 30 A/dm2 40 A/dm2 40 A/dm2 ΔE*ab 81.7P0.03%- equivalent Treatment Treatment Treatment Zn0.15%) 26000 time 0.7time 0.5 time 0.5 seconds seconds seconds Times of Times of Times oftreatment treatment treatment 3 2 2 times times times Exam- CopperGeneral 35 (Cu—Ni—Mo—Fe) (Cu—Ni—Mo—Fe) (Cu—Ni—Mo—Fe) ΔL −84.1 ple alloymetal Current Current Current Δa 2.0 18 C194 Cu- rolling density densitydensity Δb −1.0 Fe2.2%- oil film 30 A/dm2 40 A/dm2 40 A/dm2 ΔE*ab 84.2P0.03%- equivalent Treatment Treatment Treatment Zn0.15%) 26000 time 0.7time 0.5 time 0.5 seconds seconds seconds Times of Times of Times oftreatment treatment treatment 3 3 2 times times times Com- Tough General18 None None None ΔL −10.4 para- pitch metal Δa 15.2 tive copper rollingΔb 18.0 Exam- oil film ΔE*ab 25.8 ple equivalent 1 26000 Com- ToughGross 18 None None None ΔL −11.7 para- pitch rolling Δa 16.3 tivecopper + oil film Δb 21.4 Exam- Ag:180 equivalent ΔE*ab 29.3 ple ppm17000 2 Com- Tough General 18 (Cu) (Cu) None ΔL −30.5 para- pitch metalCurrent Current Δa 28.7 tive copper rolling density density Δb 18.9Exam- oil film 25 A/dm2 15 A/dm2 ΔE*ab 45.9 ple equivalent TreatmentTreatment 3 26000 time 0.7 time 2 seconds seconds Times of Times oftreatment treatment 2 2 times times Com- SUS304 General 18 (Cu) (Cu)(Cu—Co—Ni—P) ΔL −48.7 para- (Fe-Cr18%- metal Current Current Current Δa3.7 tive Ni8%) rolling density density density Δb 1.7 Exam- oil film 55A/dm2 3 A/dm2 27 A/dm2 ΔE*ab 48.9 ple equivalent Treatment TreatmentTreatment 4 26000 time 0.7 time 2 time 0.6 seconds seconds seconds Timesof Times of Times of treatment treatment treatment 2 2 2 times timestimes Com- Copper General 70 None None None ΔL −10.5 para- alloy metalΔa 15.3 tive (Cu- rolling Δb 17.1 Exam- Sn0.12%) oil film ΔE*ab 25.2 pleequivalent 7 26000 Com- Copper General 35 None None None ΔL −10.4 para-alloy metal Δa 15.2 tive C194 Cu- rolling Δb 18.0 Exam- Fe2.2%- oil filmΔE*ab 25.8 ple P0.03%- equivalent 8 Zn0.15%) 26000 Maximum surfacetemperature Surface roughness Surface Radi- of copper (measured bylaser) Surface area aton dissipation Sz Sa area ratio factor material[μm] [μm] Sku [μm²] A/B Dusting [-] ° C. Exam- 22.36 0.33 18.1255387.445 1.38 Double- 0.182 57.5 ple circle 15 Exam- 35.00 0.33 12.3559346.216 1.48 Circle 0.228 57.4 ple 16 Exam- 37.50 0.35 12.70 60152.1671.50 Circle 0.268 56.9 ple 17 Exam- 40.80 0.36 13.10 61011.751 1.52Circle 0.292 56.7 ple 18 Com- 1.18 0.13 4.08 52559.241 1.31 None 0.06859.0 para- tive Exam- ple 1 Com- 0.92 1.10 5.99 50533.462 1.26 None0.028 59.5 para- tive Exam- ple 2 Com- 4.80 0.10 5.06 51950.206 1.30Circle 0.077 58.8 para- tive Exam- ple 3 Com- 23.78 0.40 18.01 57124.7811.42 Double- 0.206 79.0 para- circle tive Exam- ple 4 Com- 1.02 0.114.23 52041.216 1.30 None 0.062 59.0 para- tive Exam- ple 7 Com- 1.050.12 4.15 52125.913 1.30 None 0.062 59.4 para- tive Exam- ple 8

TABLE 3 Thickness Type Treatment of Formation Formation Formation ofstep for copper of alloy of alloy of alloy copper copper substrate layerlayer layer Color substrate substrate [μm] (1) (2) (3) difference Exam-Corson General 35 (Cu—Co—Ni—P) (Cr—Zn) (Cr—Zn) ΔL −42.3 ple alloy metalCurrent Current Current Δa 4.7 13 (C7025 rolling density density densityΔb −6.6 Cu- oil film 45 A/dm2 2 A/dm2 1.5 A/dm2 ΔE*ab 43.1 Ni3.0%-equivalent Treatment Treatment Treatment Si0.65%- 20000 time 0.4 time 2time 1 Mg0.15%) seconds seconds seconds Times of Times of Times oftreatment treatment treatment 2 2 2 times times times Com- CorsonGeneral 35 None None None ΔL −12.1 para- alloy metal Δa 15.1 tive (C7025rolling Δb 20.3 Exam- Cu- oil film ΔE*ab 28.0 ple Ni3.0%- equivalent 5Si0.65%- 20000 Mg0.15%) Maximum surface temperature Surface roughnessSurface Radi- of copper (measured by laser) Surface area atondissipation Sz Sa area ratio factor material [μm] [μm] Sku [μm²] A/BDusting [-] ° C. Exam- 5.02 0.13 6.24 53346.639 1.33 Circle 0.102 59.7ple 13 Com- 0.97 1.10 5.54 51093.111 1.27 None 0.029 60.7 para- tiveExam- ple 5

TABLE 4 Thickness Type Treatment of Formation Formation Formation ofstep for copper of alloy of alloy of alloy copper copper substrate layerlayer layer Color substrate substrate [μm] (1) (2) (3) difference Exam-Titanium General 35 (Cu—Ni—W) (Cu—Ni—W) None ΔL −57.3 ple copper metalCurrent Current Δa 3.1 14 (C1990 rolling density density Δb −2.7Cu-Ti3%) oil film 50 A/dm2 40 A/dm2 ΔE*ab 57.4 equivalent TreatmentTreatment 26000 time 0.5 time 0.4 seconds seconds Times of Times oftreatment treatment 2 2 times times Com- Titanium General 35 None NoneNone ΔL −10.5 para- copper metal Δa 18.2 tive (C1990 rolling Δb 17.5Exam- Cu-Ti3%) oil film ΔE*ab 27.3 ple equivalent 6 26000 Maximumsurface temperature Surface roughness Surface Radi- of copper (measuredby laser) Surface area aton dissipation Sz Sa area ratio factor material[μm] [μm] Sku [μm²] A/B Dusting [-] ° C. Exam- 20.14 0.17 45.1255346.721 1.38 Circle 0.154 64.5 ple 14 Com- 1.11 0.12 4.09 52425.6211.31 None 0.065 65.8 para- tive Exam- ple 6Evaluation Results

The sample materials of Examples 1 to 18 all had satisfactory heatdissipation.

In each of the samples of Comparative Examples 1 to 3, 5 to 8, an alloylayer was not formed, and surface roughness Sz was outside the range of5 μm or more and heat dissipation was unsatisfactory compared toExamples.

The sample material of Comparative Example 4 uses a stainless steelsubstrate and showed unsatisfactory heat dissipation compared toExamples.

Furthermore, the samples of Examples were subjected to a step of formingan alloy layer on both surfaces of the copper substrate. As a result,the same properties were obtained in Examples.

What is claimed is:
 1. A copper material comprising an alloy layercontaining at least one metal selected from Cu, Co, Ni, W, P, Zn, Cr,Fe, Sn and Mo on one or both surfaces, wherein surface roughness Sz ofthe one or both surfaces, measured by a laser microscope using laserlight of 405 nm in wavelength, is 5 μm or more.
 2. The copper materialaccording to claim 1, wherein the surface roughness Sz of the one orboth surfaces, measured by a laser microscope using laser light of 405nm in wavelength, is 7 μm or more.
 3. The copper material according toclaim 2, wherein the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 10 μm or more.
 4. The copper material according to claim3, wherein the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 14 μm or more.
 5. The copper material according to claim1, wherein the surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 90 μm or less.
 6. The copper material according to claim1, wherein surface roughness Sa of the one or both surfaces, measured bya laser microscope using laser light of 405 nm in wavelength, is 0.13 μmor more.
 7. The copper material according to claim 1, wherein surfaceroughness Sku of the one or both surfaces, measured by a lasermicroscope using laser light of 405 nm in wavelength, is 6 or more. 8.The copper material according to claim 1, wherein a surface area ratioA/B of surface area A of the one or both surfaces to planarly viewedarea B, measured by a laser microscope using laser light of 405 nm inwavelength, is 1.35 or more.
 9. The copper material according to claim1, wherein color difference ΔL of the one or both surfaces based onJISZ8730 satisfies ΔL≤−35.
 10. The copper material according to claim 1,wherein color difference Δa of the one or both surfaces based onJISZ8730 satisfies Δa≤15.
 11. The copper material according to claim 1,wherein color difference Δb of the one or both surfaces based onJISZ8730 satisfies Δb≤17.
 12. The copper material according to claim 1,wherein a radiation factor of the one or both surfaces is 0.092 or more.13. The copper material according to claim 1, comprising a resin layeron the one or both surfaces.
 14. A carrier-attached copper foilcomprising an intermediate layer and an ultra-thin copper layer in thisorder on one or both surfaces of a carrier, wherein the ultra-thincopper layer is the copper material according to claim
 1. 15. A terminalusing the copper material according to claim
 1. 16. A laminatemanufactured by laminating the copper material according to claim 1; anoptional pressure-sensitive adhesive layer or adhesive layer; and aresin substrate, a substrate, a chassis, a metal processed member, anelectronic component, an electronic device, a liquid crystal panel, adisplay or a separator, in this order.
 17. A printed-wiring boardcomprising the laminate according to claim
 16. 18. A metal processedmember using the copper material of claim
 1. 19. An electronic deviceusing the copper material of claim
 1. 20. A method for manufacturing aprinted wiring board, comprising a step of preparing thecarrier-attached copper foil of claim 14 and an insulating substrate, astep of laminating the carrier-attached copper foil and the insulatingsubstrate, a step of forming a metal-clad laminate by detaching carrierfrom the carrier-attached copper foil after the carrier-attached copperfoil and the insulating substrate are laminated, and thereafter, a stepof forming a circuit by any one of a semi-additive method, a subtractivemethod, a partly additive method and a modified semi-additive method.21. A method for manufacturing a printed wiring board, comprising a stepof forming a circuit on the surface of the ultra-thin copper layer ofthe carrier-attached copper foil according to claim 14 or the surface ofthe carrier, a step of forming a resin layer on the surface of theultra-thin copper layer of the carrier-attached copper foil or thesurface of the carrier so as to bury the circuit, a step of forming acircuit on the resin layer a step of detaching the carrier or theultra-thin copper layer after the circuit is formed on the resin layer,and a step of exposing the circuit buried in the resin layer and formedon the surface of the ultra-thin copper layer or the surface of thecarrier by removing the ultra-thin copper layer or the carrier after thecarrier or the ultra-thin copper layer is detached.
 22. A secondarybattery or a supporting substrate including a copper material comprisingan alloy layer containing at least one metal selected from Cu, Co, Ni,W, P, Zn, Cr, Fe, Sn and Mo on one or both surfaces, wherein surfaceroughness Sz of the one or both surfaces, measured by a laser microscopeusing laser light of 405 nm in wavelength, is 5 μm or more.
 23. Anegative electrode current collector for a secondary battery comprisinga copper material comprising an alloy layer containing at least onemetal selected from Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn and Mo on one orboth surfaces, wherein surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 5 μm or more.
 24. A battery comprising a negativeelectrode current collector for a secondary battery comprising a coppermaterial comprising an alloy layer containing at least one metalselected from Cu, Co, Ni, W, P, Zn, Cr, Fe, Sn and Mo on one or bothsurfaces, wherein surface roughness Sz of the one or both surfaces,measured by a laser microscope using laser light of 405 nm inwavelength, is 5 μm or more.